The trends for the dissociative adsorption of CO2 exhibit a similar pattern, with dissociative adsorption energies (∆𝐺 CO 2 diss-ad ) of -3.331 eV on Rh/TiO1.69 and -2.649 eV on Rh/TiO1.98. In both cases, the dissociated *CO binds to Rh, forming a carbonyl Rh complex, while the dissociated oxygen atom remains on the titania surface. Notably, on the Rh/TiO1.98 surface, the dissociated oxygen atom fills the oxygen vacancy, effectively restoring the surface to stoichiometric TiO2. In contrast, on the Rh/TiO1.69 surface, the dissociated oxygen atom remains at the bridging site between two surface Ti cus atoms. These differences in binding behavior reveal insights into how surface reducibility and active site availability influence CO2 activation and reaction preferences.