High energy X-ray irradiation can cause physicochemical changes on the surface of some samples, causing in the obtained X-ray photoelectron spectroscopy (XPS) data cannot truly give feedback to the physicochemical state of the sample surface in the process of XPS analysis. Clarifying the influence and rules of X-ray on the physicochemical properties of the sample surface is the key to accurately obtaining XPS data. Herein, a variety of representative materials are selected to obtain the XPS analysis results under continuous X-ray irradiation, and the effect of X-ray on the physicochemical state of the sample surface is explored. The results reveal that X-ray could cause surface physical burns, thermal decomposition, destroying unstable chemical bonds, and even inducing reduction reactions for specific samples. The regularity of the influence of X-rays on the physicochemical states of the sample surface during XPS analysis and the method of reducing the influence of X-rays on the analysis results are described, which provides a theoretical support for efficient and accurate acquisition of XPS data.