Carbon-rich Si–O–C polymer-derived ceramics (PDCs) were investigated by various spectroscopic techniques, in order to characterize the evolution of their predominantly amorphous microstructure upon thermal treatment up to 1450°C. Particular attention was addressed to modifications of the excess free carbon phase present in these materials. Surprisingly, the carbon clusters exhibited high stability above the pyrolysis temperature. Despite the high volume fraction of carbon, only a very limited carbothermal reduction process was detected. This study is divided into two parts: PartI deals with characterization tools that reveal a rather low lateral resolution and are hence termed here as integral spectroscopic techniques, i.e., solid-state NMR and Raman spectroscopy. In contrast, PartII illustrates the experimental results obtained from the very same materials characterized by spectroscopic and imaging techniques with high lateral resolution, i.e., electron energy-loss spectroscopy (EELS), high-resolution transmission electron microscopy (HRTEM), and energy-filtered TEM. In addition to materials characterization, emphasize of both papers is also to compare the information gained by either integral or local spectroscopy techniques and to highlight the strengths and weaknesses of either approach.