Photocatalytic CO₂ reduction into renewable hydrocarbon solar fuels is considered as a promising strategy to simultaneously address the global energy and environmental issues. In this study, a binary g-C₃N₄/ZnO photocatalytic system was constructed via a one-step facile calcination method and further used as a photocatalyst for CO₂ reduction. It was shown that the as-prepared g-C₃N₄/ZnO photocatalytic system exhibited enhanced photocatalytic activity for CO₂ reduction by a factor of 2.3 compared with pure g-C₃N₄, while maintaining the original selectivity of pure g-C₃N₄ to convert CO₂ directly into CH₃OH. For the first time, the coupling effect of ZnO responsible for the improved photoactivity of g-C₃N₄ was fully illustrated and a direct Z-scheme mechanism rather than the conventional heterojunction-type mechanism was proposed to explain the better performances of the g-C₃N₄/ZnO binary composite photocatalytic system. The enhancement of photocatalytic CO₂ reduction activity is attributed to the highly efficient ZnO-to-g-C₃N₄ electron transfer occurring at the intimate contact interface between the g-C₃N₄ phase and ZnO phase. This work will provide new deep insights into the rational construction of a g-C₃N₄-based photocatalytic system and the design of a direct Z-scheme system without an electron mediator for photocatalytic CO₂ reduction reactions.