Because the surface properties of biomedical metallic materials determine their biological properties, it is very important to elucidate the physical and chemical properties of biomedical metallic materials and to reveal the interaction mechanisms between the surface interface and the body through advanced characterization techniques. X-ray photoelectron spectroscopy (XPS) is a powerful surface analysis technique which can be used for qualitative and semi-quantitative analysis of elements and valence states on material surface with high sensitivity and resolution. Combined with ion beam sputtering and angular resolution depth analysis, the depth distribution information of the surface layer can be obtained. XPS surface analysis technique has been widely used in the research of biomedical metallic materials. In this paper, firstly, the principle and characteristics of XPS are briefly introduced. Secondly, according to the classification and research field of biomedical metallic materials, the application of XPS surface analysis technique in the design, manufacture, surface modification and surface interface characterization of biomedical stainless steel, biomedical cobalt-based alloys, biomedical titanium alloys and biomedical magnesium alloys are mainly discussed. By summarizing the advantages and disadvantages of the above work, it further clarifies the application potential of XPS surface analysis technique in small area, chemical imaging, angle resolution, in-situ testing, valence band spectrum, synchrotron radiation excitation source and other aspects. Finally, the prospect and suggestions for the development and application of new biomedical metallic materials assisted by XPS technique are put forward.