The aging of paper relics has always been an important research problem in conservation. Previously, the aging of paper was assessed by visual observation, and was often based much on the overseers’ experience. The physical strength and degree of polymerization could not be tested because of the shortage of large numbers of suitable paper samples. In recent years, with the development of new analytical tools, including micro-confocal microscopy, near infrared Fourier transform and surface enhanced Raman spectroscopy, Raman-based spectroscopic methods have been more and more often used for the in-situ, non-destructive microanalysis of old paper relics. Some recent applications of Raman spectroscopy to the analysis of paper degradation and of carbon-based black and other pigments, as well as their relevant research status, are reviewed in this paper. With more research, Raman could also be used with other analytical techniques and quantitative methods. Raman spectroscopy will continue to play an important role in the study of paper relics.