A method for evaluation of uncertainty was established with standard deviation of relative error. Utilizing a polarized energy dispersive X ray fluorescence spectrometer(P-EDXRF)X-lab 2000 with pressed polyethylene-backed pellets, 76 national reference materials and 89 geological examination samples were analyzed, the results indicated that the relative errors consist with the normal distribution with confidence level 95%. The section standard deviations of relative errors acted as method global relative uncertainty and expanded factor was 2. The section relative uncertainty caused by precision was analyzed and relative uncertainty caused by accuracy based on the error transfer formula was isolated. The ratio of relative uncertainty caused by accuracy to the global relative uncertainty was different with different levels and elements. Two methods validated that the evaluation of global uncertainty is reasonable, with the first method being the formula of audited results in laboratory, and the second being the comparison of standard value with expanded uncertainty and a revised value with expanded uncertainty.