<p>Artificial photosynthesis, converting CO₂ and H₂O into solar fuels, is considered as a strategic pathway to alleviate the greenhouse effect and the energy crisis. Nonetheless, in many heterojunction-based artificial photosynthetic systems, the CH₄ productivity is significantly limited by poor carrier transport, narrow spectral light absorption, and lacking suitable active sites for the eight-electron reaction. Herein, a MoO_2−<i>x</i>/Bi₂MoO₆ (MO/BWO) Schottky junction with a strong interfacial coupling effect was fabricated by a two-step hydrothermal strategy. The optimized MO/BMO Schottky junction delivered a CO₂-to-CH₄ photoreduction rate of 23.3&#xa0;μmol&#xa0;g⁻¹ with 90.7% selectivity. In situ X-ray photoelectron spectroscopy and theoretical calculation demonstrated that BMO interacted with MO to produce a strong electron coupling effect and form a Schottky junction, which promoted the facilitated the directional migration of photogenerated electrons from BMO to MO with prolonging average photogenerated charge lifetime from 26.6 to 48.7&#xa0;ps, but also effectively suppressed electron backflow through the Schottky barrier. Moreover, the coupling of MO with BMO significantly reduced the energy barrier of the rate-determining step. This work delves into the role of non-precious metal-based Schottky junction design in enhancing photocatalytic CO₂ reduction performance, providing new insights into co-catalyst as active sites for CH₄ generation in the CO₂ photoreduction process.</p> Graphical abstract <p>A MoO_2−<i>x</i>/Bi₂MoO₆ (MO/BWO) Schottky junction with strong interfacial coupling effect was fabricated, which enhances the facilitated the separation of photogenerated carriers charge lifetime; thus, facilitates photocatalytic CO₂ reduction activity.</p> <p></p>