The Thousand Buddha Grotto is located in Sichuan north of Guangyuan and east of the Yangzi River. Currently, there are 54caves, 819niches and more than 7,0statutes preserved there. These are precious cultural heritage with very high art and research value. Seven samples of green pigment from the ThousandBuddha Grotto were analyzed by metallographic microscopy, polarized microscopiy, and Raman spectroscopy to determine its composition and constitution. It was found that green pigments from ThousandBuddha Grotto were synthetic atacamite and malachite. A small amount of emerald green was also found in the outermost layer, which may have been applied in recently for restoration. The history, characteristics and use of manmade copper trihydroxychlorides pigment and related substances, malachite and emerald green, in China are discussed in this article, which provides help to the later protection work.