A Re catalyst supported on TiO2 (Re/TiO2) promoted the reverse water-gas shift (RWGS) reaction, exhibiting high selectivity toward CO. Operando X-ray absorption near edge structure (XANES) measurements revealed that the redox of Re species was responsible for promotion of the reaction. The Re/TiO2 catalyst also possessed remarkable durability and maintained >99.9% CO selectivity for more than 1000 h.