Selective CO₂ hydrogenation into CO via reverse water-gas shift (RWGS) reaction is a pivotal route for large-scale carbon abatement, yet remains hindered by the scarcity of efficient and scalable catalysts. Here, we report the construction of a high-performance Ni/TiO₂ catalyst by encapsulating in an in-situ created, robust carbon layer for boosting CO₂ conversion and CO selectivity. Mechanistic studies reveal that the catalyst operates via a redox pathway, wherein CO₂ dissociates into CO at oxygen vacancies on the TiO₂ surface, followed by vacancy regeneration through hydrogen dissociated on Ni. Within this framework, the carbon overlayer fulfills two promotional roles: it drastically lowers the hydrogen diffusion barrier, establishing a spillover “highway” on TiO₂ that generates abundant and distal oxygen vacancies to enhance CO₂ conversion; Concurrently, it blocks interfacial charge transfer to inhibit CO adsorption on Ni, which suppresses methanation and CO disproportionation, thereby boosting CO selectivity. Advanced characterization further demonstrates that the exceptional durability of the carbon overlayer, rooted in the dynamic carbon equilibrium induced by surface Ni-C species during the RWGS reaction, enables sustained efficient hydrogen activation and spillover (thereby preserving enhanced oxygen vacancies) and persistent inhibition of CO adsorption. These synergistic advantages endow the carbon-coated Ni/TiO₂ catalyst with outstanding RWGS performance, achieving equilibrium CO₂ conversion with nearly 100% CO selectivity for over 500 hours under industrially relevant conditions. Constructing efficient carbon overlayer to selectively modulate the surface reactivity may provide a promising avenue for the design of high-performance and cost-effective catalysts for sustainable chemical processes.