In the history of Chinese pigment, copper green, a pigment, was used in vast territory and for a long time. In the present paper, the nature, spectral characteristics, thermodynamic stability of the four isomers of the basic copper chlorides and also their application in the polychrome relics were discussed. The four isomers can be identified quickly by Raman spectral analysis which is a micro-damage or even a nondestructive technique. The order of their thermodynamic stability is as follows: clinoatacamite＞paratacamite＞atacamite＞botallackite. It was showed that in the relics samples copper green was mostly botallackite and atacamite which were less stable isomers. According to the Ostwald step rule, the environmental monitoring should be strengthened to prevent the change in their physical and chemical structures.