Natural photosynthesis proceeded by sequential water splitting and CO2 reduction reactions is an efficient strategy for CO2 conversion. Here, mimicking photosynthesis to boost CO2-to-CO conversion is achieved by using plasmonic Bi as an electron-proton-transfer mediator. Electroreduction of H2O with a Bi electrode simultaneously produces O2 and hydrogen-stored Bi (Bi-Hx). The obtained Bi-Hx is subsequently used to generate electron-proton pairs under light irradiation to reduce CO2 to CO; meanwhile, Bi-Hx recovers to Bi, completing the catalytic cycle. This two-step strategy avoids O2 separation and enables a CO production efficiency of 283.8 μmol g-1 h-1 without sacrificial reagents and cocatalysts, which is 9 times that on pristine Bi in H2 gas. Theoretical/experimental studies confirm that such excellent activity is attributed to the formed Bi-Hx intermediate that improves charge separation and reduces reaction barriers in CO2 reduction.