High-resolution X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) were used to characterize IrO₂(110) films on Ir(100) with stoichiometric as well as OH-rich terminations. Core-level Ir 4f and O 1s peaks were identified for the undercoordinated Ir and O atoms and bridging and on-top OH groups at the IrO₂(110) surfaces. Peak assignments were validated by comparison of the core-level shifts determined experimentally with those computed using DFT, quantitative analysis of the concentrations of surface species, and the measured variation of the Ir 4f peak intensities with photoelectron kinetic energy. We show that exposure of the IrO₂(110) surface to O₂ near room temperature produces a large quantity of on-top OH groups because of reaction of background H₂ with the surface. The peak assignments made in this study can serve as a foundation for future experiments designed to utilize XPS to uncover atomic-level details of the surface chemistry of IrO₂(110).