As part of the Topical Collection on the archaeometric study of ceramics, this paper focuses on terra sigillata ware. The main aims are to provide a review on the state of the art of the studies and to provide a guide to the most suitable analytical techniques. The text is divided into four main parts: (1) a brief archaeological introduction on the ancient production of terra sigillata; (2) a summary of the archaeometric studies carried out to date; (3) a reasoned list of the most suitable techniques for the investigation of the ceramic body and (4) an in-depth discussion on the most effective techniques for the study of the coating. The application of both destructive and non-destructive techniques is critically evaluated as well as the advantages and disadvantages provided by the different instrumentation, in terms of sample preparations and expected results.