Co₃O₄ has displayed promising ability for 5-hydroxymethylfurfural (HMF) electrooxidation reaction (HMFOR), which is an efficient way to produce high-value chemicals. However, its poor intrinsic ability has seriously limited its electrochemical performance. The introduction of foreign components into Co₃O₄via heterophase interfacing is an efficient strategy to enhance its intrinsic activity. Herein, we have modified Co₃O₄ through the fabrication of the heterophase interface between Cu-doped Co₃O₄ (Cu−Co₃O₄) and CuO (Cu−Co₃O₄/CuO). With the introduction of Cu species, the electronic structure of the electrocatalyst has been well-modulated, whose electrons were preferentially transformed from Co to Cu atoms, suggesting a strong electron interaction. The electrochemical results suggest that Cu−Co₃O₄/CuO exhibited a lower overpotential, faster reaction kinetics, and higher turnover frequency than Cu−Co₃O₄ and pure Co₃O₄. Experimental results and theoretical calculations demonstrate that the fabrication of the heterophase interface could have strong adsorption toward HMF owing to the enhanced interaction with the aldehyde and hydroxymethyl groups. Furthermore, Cu−Co₃O₄/CuO possessed a relatively poor reliance on the furan ring for HMF adsorption but accelerated the oxidation of the aldehyde group. This work provides a significant reference for the development of efficient HMFOR electrocatalysts.