A series of standard samples with different component contents were prepared by simulating the composition of hydro-fining catalyst,and the matrix effect was corrected by empirical coefficient method.Then a method for the content determina-tion of nickel,molybdenum,tungsten and phosphorus in hydrofining catalysts was established by X-ray fluorescence spectro-metry.The determination range（mass fraction） is as follow：w（NiO）=1.92%~7.1%,w（MoO₃）=8.80%~13.69%,w（WO₃）=8.81%~14.50% and w（P₂O₅）=2.04%~6.96%.This method has high accuracy and precision that the correlation coefficients of the four quantitative calibration curves established by this method were all higher than 0.999 and the relative standard deviation of the determination result was less than 1%,which met the needs of scientific research and industrial production.