Supported rhenium (Re) catalysts are emerging as promising candidates for hydrogenation reactions, which are crucial in industrial processes such as biomass valorization, CO2 reduction, and petroleum refining. However, despite their broad application, the structural and mechanistic understanding of these systems remains limited. The strong oxophilic nature of Re, combined with its ability to adopt multiple oxidation states, complicates the characterization of the active species even with advanced experimental techniques. In this study, we employ density functional theory calculations, alongside ab initio thermodynamic analysis, to systematically explore the structural and electronic properties of single-atom Re catalysts on a TiO2 surface, providing insights that could inform the rational catalyst design. Our calculations reveal the formation of stable Re polyhydrides on the surface under hydrogen-rich conditions. Notably, even in highly reducing environments, Re species with low formal oxidation states are thermodynamically unfavorable. The stable Re species identified on TiO2 surfaces demonstrate high reactivity toward CO2 hydrogenation. The electronic properties and computed X-ray photoelectron spectroscopy (XPS) signatures of the feasible surface species are highly influenced by the ligand environment. This work highlights the limitation of routine interpretation of experimental XPS characterization data in terms of the formal oxidation state.