Abstract: A method for the determination of major elements including Si, Al, Fe, Ca, K, Mg and Na in shale samples by X-ray fluorescence spectrometry with fused glass disc sample preparation was reported in this paper. The shale, rock, sediment and soil National Standard Reference samples were used as the calibration standards. The matrix effect was corrected with theoretical alpha coefficient and empirical coefficient methods. The precision of the method is ≤1.50%RSD (n=12). The method has been applied to the determination of these major elements in shale samples and the results are in agreement with those by chemical methods.