CO2 photocatalytic reduction into reusable carbon forms via photocatalyst is becoming increasingly attractive, providing feedstock for industrial production and daily life. However, most of these materials face the challenge of rapid recombination of charge carriers and deficient active sites, thus severely restricting the catalytic performance. Herein, a new strategy of interweaving Bi2S3 and UiO-66 via bulk-doping was established to enhance the charge transfer in Bi2S3/UiO-66, and a photothermocatalytic CO2 reduction process was also adopted to instead of traditional photoreduction, with the aim of greatly increasing the separation efficiency of electron-hole. Upon irradiation of UV–vis-IR light, the optimized catalyst possesses an impressive CO production rate (rCO =25.60 μmol g-1 h-1) and the good durability (at least for five cycles) without using any sacrificial agents. The efficient catalytic performance for CO2 reduction over the catalyst originates from thermally-assisted photocatalytic behavior.