It is now almost a hundred years since the Raman Effect was discovered. The change in emphasis of the requirements for sampling for Raman spectral data are reviewed in the light of new discoveries for the improvement of technology concerned. Landmark applications in this regard of the adaptation of the laser, microscope and recording advances such as the use of Notch filters and coupled charge-transfer diodes are surveyed and the influence of the miniaturisation of the instrumentation to hand-held devices is recounted. The future application of Raman spectroscopy to cultural heritage artefacts and relevant materials is also described and some of the drawbacks and pitfalls to its further advancement are highlighted. Hence, much of the earlier Raman work in the area of cultural heritage involved pigments in oil paintings and on historiated manuscripts, which could be undertaken in the laboratory before restoration or conservation work. The next stage of applicability would be two-fold in concept ; firstly, the adoption of long wavelength laser excitation with Fourier transform interferometry to access biological materials and their degradation which generally produced high levels of background fluorescence which obviated the recording of the Raman spectra using visible excitation, and the miniaturisation of laboratory equipment which enabled the carriage of Raman spectrometers to be made into museums and secure areas from which cultural heritage artefacts could not be removed and for which the taking of excised specimens was expressly forbidden. This new generation of Raman spectrometers immediately found a welcome audience with a wider analytical repertoire and has now progressed to the ultimate in hand-held portable devices for use in the field for geology, forensic science, HAZMAT security in airport screening, crime scene analysis, archaeology, museology and planet exploration. The non-invasive identification of some phases of matter, crystalline or amorphous, inorganic or organic is the strong point of Raman microspectroscopy. It is now possible to work with sample powers of less than 0.1 mW, or even 0.01 mW, which guarantees the absence of disturbance from strongly colored/absorbing materials. For moderate powers the recording time can be less than a second, which makes it possible to image larger surfaces and produce maps of molecular species and their spatial arrangement on the surfaces of specimens. A very good example of this application for cultural heritage studies is the distribution of components of pigment mixtures on the surface of an artefact , especially if accomplished in situ on a historiated manuscript or a piece of porcelain. The ease of performing measurements paradoxically becomes one of the weaknesses of current and probably future Raman analyses. The SERS effect was discovered more than 40 years ago and offered some perspective to identify dyes in small concentration on substrates. The preparation of silver colloids and the reproducibility control of their effectiveness and stability over time is more of an art than science. The development over several years of specific substrates prepared by microelectronic techniques for the detection of pollutants or toxic products could help future applications in the field of Cultural Heritage. If successes have been obtained for the detection of traces in liquid phases (e.g. often better than 10-3 moles/l), it is more difficult in the solid phase and especially when several compounds are present. The 23 chapters of the book are: 1. Foreword, 2. Historical Overview of Raman Spectroscopy, 3. Theory of Raman Spectroscopy and Raman instrumentation, 4. Combination of Raman spectroscopy with Other Techniques (XRF, SEM-EDAXS, IR...), 5. Pigments, Dyes and Colouring Agents, 6. Cultural Heritage Meets the Art Forensics Enigma: Raman Spectroscopic Authentication and the Exposure of Fakes and Forgeries in Art Works, 7. Jewellery and Gemstones, 8. Cave Paintings and Rock Art, 9. From Frescoes to Paintings, 10. Analytical Raman Spectroscopy of Manuscripts and Maps : The Role of Inks, 11. Patina, corrosion and conservation treatments, 12. Glass, Pottery and Enamelled Artefacts, 13. Archaeology of Biomaterials : Mummies ,Ivories , Resins and Textiles, 14. Raman Spectroscopy and Industrial Archaeology, 15. Case Study: Raman Spectroscopic Analysis of a Putative 17th Century Oil Painting Depicting William Shakespeare, 16. Case Study : “Noli Me Tangere”: A Renaissance Original? A Holistic Analytical Spectroscopic Challenge, 17. Case Study: Raman Spectroscopic Analysis of Welsh Porcelains, 18. Case Study - In-field and On-site Raman Analysis, 19. Case Study: Non-invasively Documenting the Transfer of Enamelling Technology from Europe to China and Japan. The Role of the Jesuits in the 17th Century, 20. Case Study : The Shroud of Turin – Iconic Relic or Fake? The Role of Raman Spectroscopic Analysis in Its Forensic Appraisal, 21. Case Study : A Unique Rockingham English Porcelain Table : A Holistic Forensic Appraisal, 22. A Little Knowledge is A Dangerous Thing: A Miscellany of Faux-Pas in the Cultural Heritage of Literature, 23. Raman Analysis: What is Straightforward, What is Difficult and Future Perspectives and Index. The software of the miniaturized instruments operates in a mode that strongly amplifies the signal with the subtraction of a 'background' which actually contains certain information for a specialist. Likewise, broadbands may be discarded in this instrument-generated subtraction. Similarly, the variable penetration of light in different, colored phases, and the very large differences in the Raman scattering efficiency of these phases, even in the absence of resonance effects, mean that the images obtained by Raman mapping can be misleading: the importance of phases that produce a strong signal is over magnified by the instrument software. Some phases are very sensitive to laser illumination, with the onset of thermal heating, which causes phase changes, oxidation, degradation of the target specimen etc. The ease of use of the database, with an automatic search algorithm, is very effective for industrial research where the questions are formulated precisely between a limited number of possible configurations. However, in the field of cultural heritage it must be used with care because of the modifications of intensity that may be inherent due to the effects of species orientation when the complex physics controlling the Raman Effect and scattering vectors must be taken into account. In researching cultural heritage materials and artefacts, one should also be aware of the possibility of finding some new material whose presence might initially not have been suspected and this would not have been registered in the instrument database. A good example of this would be novel pigments, pigment mixtures and binders in old paintings. While Raman spectral studies concern both natural biological and synthetic technological compounds, the simulation of Raman spectra by ab initio calculation, DFT (Density Functional Theory), etc. is common, this type of approach remains very marginal for applications in Cultural Heritage. Certainly this will be addressed in the future and will bring a new slant on the analysis of cultural heritage materials. Nevertheless, in our experience the use of initial in situ measurements , despite their obvious potential drawbacks in the amount of analytical data that can be accessed there from , can reveal surprises about the specimen that were not at first suspected by the museum conservators, who then agree to a strictly limited sample excision from the artefact ( which was initially forbidden) to verify important potential conclusions for its conservation and restoration using laboratory-sited instrumentation. In other words, the miniaturised Raman instruments act as a first-pass screening mode for the taking of limited samples for the subsequent in-depth spectroscopic analysis in the analytical laboratory. This is not exceptional and has been found to occur quite frequently in the cultural heritage area within the experience of the authors here.