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BACKGROUND: The quantification of trace elements m geological samples depends largely on the analytical methods that require complex chemical pretreatment. High - energy polarized energy - dispersive x - ray fluorescence spectrometer ( HE - P - EDXRF) has a considerable advantage for the determination of trace elements with large atomic number because of its high - energy properties, which can effectively excite the Ka line of heavy elements. OBJECTIVES: To establish a HE - P - EDXRF method for quantitative analysis of major and trace elements m geological samples. METHODS: Different types of first - class standard materials ( soil, rock and sediments) were used to obtain good linear coefficients of standard materials curves. To reduce the spectral interference, Ka line of heavy elements were selected for a better accuracy and detection limits. Matrix correction method can greatly improve the fitting effect of the calibration curve, combination matrix correction approach of Alpha calibration mode and Compton calibration mode were applied on Pb and Zn. The performance of analytical method was evaluated by uncertainty. RESULTS : Selecting Ka line as analytical line for analysis of heavy elements can achieve a better result, even some rare earth elements can be measured accurately, with the average relative errors of La, Ce and Nd being 6. 20%, 3. 02% and 4. 75%, respectively. Detection limit of trace element Ba and rare earth elements ( such as La, Ce) from EDXRF has obvious advantages comparing with that from WDXRF, whereas the detection limit for light elements from WDXRF are lower. For all the major and trace elements, relative average error of test training data was less than 15% except for Na2 0, MgO, P and Sm. The relative average error of trace elements was between 2. 40% and 16. 3%. The accuracy of trace elements ( except Cu and Yb) are significantly better than that of WDXRF. According to quantifying uncertainty in analytical measurement, no significant difference exists between the trace elements results ( except V and Th) and the recommended value of certified reference materials. CONCLUSIONS: HE - P - EDXRF is a simple, fast and environment - friendly method that can analysis multielement simultaneously in geological samples. This method is suitable for the trace and rare earth elements quantification in rock, soil and sediment so that overcome the dependence of quantitative analysis these elements on methods requiring priori chemical treatments. [ABSTRACT FROM AUTHOR]