The method for quantitative analysis and depth profile analysis of Cu（In,Ga）Se2（CIGS） solar cell films was established using X-ray photoelectron spectroscopy（XPS） based on international key comparison K129 participated by National Institute of Metrology（NIM）.The depth sputtering and spectrum acquisition were carried out by using suitable conditions which were obtained through pre-research.The data analysis processes included determination of signal intensity using total number method,determination of relative sensitivity factor,atomic fraction and uncertainty.By using the data processing,a reliable and effective film composition could be obtained.The results indicated this method had a good repeatability with RSD less than 2% in 5 measurements.The atomic fractions of Cu,In,Ga and Se were measured accurately with expand uncertainties less than 4%,which was consistent with those obtained by other national metrology lab.In addition,the analytical result calculated from 4 different sensitivity factors which were obtained from reference sample and instrumental database were compared.The results showed that the values of sensitivity factors from instrumental database modified by the manufacturer were closer to the values obtained from the reference sample,thus the sensitivity factors from instrumental database modified by the manufacturer could be used for the quantitative analysis of atomic composition of alloy films with XPS.The method could be used for the composition measurement of a lot of films with accurate improvement with surface analytical techniques.