The Thousand Buddha Grotto is located in Sichuan north of Guangyuan and east of the Yangzi River. Currently, there are 52 caves, 819 niches and more that 7,000 statues preserved there. These are precious cultural heritage with very high art and research value. Seven samples of green pigment from the Thousand-Buddha Grotto were analyzed by metallographic microscopy, polarized microscopy, and Raman spectroscopy to determine it composition and constitution. It is found that green pigments from Thousand-Buddha 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 man-made 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.