Abstract: Based on 23 national standard materials of biological component such as rice, wheat and corn, this paper discusses the application of X-ray Fluorescence Spectrometry (XRF) for the analysis of major and minor elements in biological samples. After a selection of analysis conditions such as stimulation current and voltage, analysis line, background, interrupting element spectrum line, analysis crystal, collimator, and pulse height distribution (PHD), the pressed powder pellet technique was used to prepare standard samples. Correction of work curve, element inter-element absorption effect and spectral line overlap effect were obtained by the regulation method and the internal standard method of Rh Kα (from the X-ray tube target) Compton-scattered radiation. The results indicate that the national standard material of biological component serial was appropriate both in content range and gradient for the common biological sample analysis. The detection limit verifies the validity of the measured results, with the precision of 2.62%-14.79%, and the measured result being consistent with the certified value. X-ray fluorescence spectrometric method is simple, sensitive, and accurate in biological sample analysis. The accuracies of the experiment meet the requirements for common biological sample analysis.