Catalytic reduction of CO₂ with renewable H₂ to CO via the reverse water gas shift (RWGS) reaction is an attractive approach to recycle CO₂ and control net emission of CO₂ to atmosphere. However, low activity and high CH₄ selectivity at low temperatures limited the practical implementation of the reaction. Herein, Pt-Re/SiO₂ catalysts with varying amount of Re were prepared with co-impregnation and tested for the RWGS reaction. Characterization results indicated that the oxophilic ReO_x (0 ≤ x ≤ 3.5) located in close proximity to Pt particle, modified the surface of Pt by both partial coverage and electronic interaction, resulting in the reduced number of sites for and weakened strength of CO adsorption. At 400 °C, the turnover frequency (2.30 s⁻¹) on the optimal Pt-Re/SiO₂ catalyst (Pt/Re = 1.91) is 3.9 times higher than that on Pt/SiO₂ under differential conditions, and the apparent activation energy is lowered. In contrast to Re/SiO₂ which produces significant amount of CH₄, the CO selectivity on Pt-Re/SiO₂ maintained > 96.2 % under integral conditions. Reaction order analysis revealed that Pt facilitates H₂ activation whereas the oxophilic ReO_x enhances CO₂ adsorption and activation. The perimeter sites at the Pt/ReO_x interface with a balanced hydrogenation and C-O cleavage properties synergistically improve the RWGS activity while inhibiting CH₄ production.