Abstract Support effects critically influence the electronic structure and catalytic behavior of heterostructure catalysts, yet the fundamental physicochemical principles governing interfacial charge polarization and its impact on reaction selectivity are not fully understood. Here, we reveal how interfacial electronic induction propagates across metal sulfide–oxide junctions by using CO 2 hydrogenation over MoS 2 /metal‐oxide heterostructures as a model system. By constructing a controlled electronic gradient across oxide supports, we introduce the concept of an interfacial inductive effect—the σ‐bond inductive effect analogous in organic chemistry—to describe how charge transfer (Δ q ) at Mo‐edge sites modulates intermediate adsorption and reaction branching. Combined spectroscopy and density functional theory establish a quantitative Δ q – ε d – E ads relationship, demonstrating that interfacial polarization tunes the d‐band center and MoCO antibonding occupation, thereby governing CO* binding and C 1 product distribution. This study translates a molecular electronic principle to heterogeneous interfaces, offering a mechanistic and generalizable design rule for steering catalytic selectivity through interfacial electronic induction.
Tian et al. (2026) studied this question.