Efficiency of solar-driven CO2 into fuels is largely limited by the sluggish reaction kinetics resulting from high activation barriers and poor electron-hole separation. Here, a synergistic strategy was proposed to overcome these obstacles. As a prototype, KOH-modified Ni/LaTiO2N photocatalyst afforded a high performance in CO2 reduction with a generation rate of 9.69 mu mol g(-1) for CH4 and 0.31 mu mol g(-1) for CO, about 5 times higher than the catalytic activities of LaTiO2N. The prominent enhancement results in the following effects: (1) Schottky barrier at Ni/LaTiO2N interface boosts separation of electron-hole pairs. (2) The OH- of KOH as basic sites favors activation of CO2 into CO32- species, significantly improving the reaction kinetics of CO2 reduction. (3) The OH- also functions as hole acceptor, boosting the proton release from H2O oxidation.