The chromogenic copper and arsenic-containing green and blue-green pigments of rock carvings at Big Buddha Bay in Dazu, Chongqing, were investigated and analyzed using portable X-ray fluorescence spectrometry (XRF), portable microscopy and other non-destructive analysis methods in combination with X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX), X-ray photoelectron spectrometry (XPS) and micro Raman spectrometry (RM). The results show that the chromogenic component of the green pigment is emerald green , and that of blue-green pigment is lavendulan [NaCaCu₅(AsO₄)₄Cl·5H₂O]. Also, it is inferred that lavendulan is a discoloration product of emerald green, based on this research. This work provides new clues to and methods for research on the chromogenic changes in modern synthetic pigments.