X-ray photoelectron spectroscopy (XPS) is an efficient technique for recognizing the state of elements. However, the effects of X-ray irradiation on change in the chemical state are sometimes ignored, which may impair the understanding of the environmental behavior of these elements. This study determined the change in the U 4f spectra induced by X-ray irradiation during XPS detection. For U(VI) on non-semiconductors, X-ray irradiation led to a negative shift of U 4f7/2 to ∼ 380.8 eV due to the break of the uranyl molecules, but not resulting in U(IV) species. However, owing to the photocatalytic reduction of U(VI), the irradiation of U(VI) loaded semiconductors rapidly induced the negative shift of U 4f7/2 peak to ∼ 379.8 eV, which is the characteristic of U(IV). Moreover, apparent photo-reduction occurred even if the samples were far from the center of the X-ray beam (>3971 μm). Based on these findings, methods for reducing potential error due to X-ray irradiation are suggested, including using the minimum scan time, measuring uranium-containing samples first or independent of other samples, and using X-ray of lower intensity. The results indicated that X-ray induced alteration to the chemical states must be considered when using X-ray techniques.