A new quantitative analysis method was established for the determination of Fe and Ba in BaFe12O19 samples by binary ratio and X-ray fluorescence spectrometry. The calibration curve was established by a self-made pure Fe powder(AR) and pure BaCO3 powder(AR) standard sample which was prepared by powder pellet method. The standard sample has the content of Fe 75% and the content of Ba is 17.4% for the validation sample to verify the calibration curve fitting. Through the analysis the Fe and Ba content in the validation samples is 75.68% and 16.92%, the relative standard deviation is 0.317% and 1.11% respectively, The working curve has a good linear relationship with high accuracy and good precision. The experiment measured The content of Fe and Ba in BaFe12O19 sample was measured in the experiment to be 57.28% and 13.42%, and the relative standard deviation is 1.05% and 0.73%, respectively.