Pigments are important material composition and artistic expression of polychrome cultural relics. The protection of cultural relics pigments has always been a hot and difficult issue in the field of cultural heritage protection. Cultural relics have non-regenerative characteristics, so the in-situ, non-invasive and accurate analysis of micro samples of cultural relics pigments plays an important role in protection of cultural relics. With the progress of various micro-beam technologies, micro spectral analysis technologies have unique advantages in the study of cultural relic the protection with the working mode of precise micro-area positioning and rapid spectral scanning, so the application has been developed rapidly. This paper presented the application, characteristics, and technical difficulties of the micro spectral analysis technologies, such as micro X-ray fluorescence(μ-XRF), micro-laser induced breakdown spectroscopy(μ-LIBS), micro-Raman spectroscopy(μ-Raman), micro-Fourier transform infrared spectroscopy(μ-FTIR), micro X-ray absorption near-edge spectroscopy(μ-XANES), micro time-resolved photoluminescence microscopy(μ-TRPL) and micro-fade tester(μ-FT) in order to get the information about composition analysis, depigmentation and degradation analysis, and protective effect evaluation. Also, the development tendency of microspectral technologies was prospected from eliminating measurement interference, improving measurement devices, and developing hybrid setup. Among these micro spectral technologies, μ-XRF, μ-LIBS, μ-Raman and μ-FTIR are conventional technologies for pigment composition analysis. Moreover, μ-Raman and μ-FTIR are widely applied to assess protection effect and μ-FTIR and μ-XRF can also be used to analyze degradation products. Combined with PCA and other relevant analyses, conventional micro spectral technologies can be used to identify the pigments of cultural relics and to provide valuable information for the origin, dating and authenticity identification of cultural relics. Especially, μ-XANES, μ-TRPL and μ-FT belong to the advanced international technologies which play a key role in the analysis of cultural relics pigments, the identification and visualization of distributions of the degradation products, the origin of the pigment and its history, degradation phenomena associating with the migration of ions from pigments and specific photochemical fading behavior. However, at present, these advanced technologies are rarely applied in the field of cultural relics protection in China. Therefore, this study has great significance for promoting the development of analysis and protection of cultural relics and brings a new insight into the identification, protection and restoration of cultural relics pigments in China.