The authors tried to find a method for quantitative analysis using pXRF without solid bulk stone/jade reference samples. 24 nephrite samples were selected, 17 samples were calibration samples and the other 7 are test samples. All the nephrite samples were analyzed by Proton induced X-ray emission spectroscopy (PIXE) quantitatively. Based on the PIXE results of calibration samples, calibration curves were created for the interested components/elements and used to analyze the test samples quantitatively;then, the qualitative spectrum of all nephrite samples were obtained by pXRF. According to the PIXE results and qualitative spectrum of calibration samples, partial least square method (PLS) was used for quantitative analysis of test samples. Finally, the results of test samples obtained by calibration method, PLS method and PIXE were compared to each other. The accuracy of calibration curve method and PLS method was estimated. The result indicates that the PLS method is the alternate method for quantitative analysis of stone/jade samples.