Hyperspectral imaging instrumentation was used to collect the spectral and spatial information on a modern Chinese painting. The spectral angle mapper (SAM) was selected to classify and identify the pigments used in the painting. The classification and identification results with actual pigments used are compared. It is found that in order to achieve more satisfactory results different threshold values must be assigned due to the different characteristics of the pigments. The threshold value could be ascertained by studying the mean spectrum of different classes in comparison with the standard pigments data base. Some technical details of SAM are discussed in order to provide data support for future studies on identification of pigments used in Chinese relic paintings.