<p>The development of highly active, low-cost, and durable electrocatalysts is crucial for the efficient glycerol oxidation reaction (GOR). Herein, a Cu-doped, self-supported NiCo₂O₄ nanosheet array catalyst grown on nickel foam (Cu-NiCo₂O₄/NF) was fabricated through a simple electrodeposition method followed by thermal annealing. The resulting nanosheet arrays are uniformly anchored on the conductive NF substrate, forming a three-dimensional nanoflower-like architecture that offers abundant accessible active sites and enhanced electronic conductivity. Moreover, Cu doping effectively tailors the electronic structure of NiCo₂O₄, optimizing the adsorption and transformation of key glycerol oxidation intermediates. This synergistic effect significantly lowers charge transfer resistance and promotes rapid electron transport. Benefiting from these structural and electronic advantages, the Cu-NiCo₂O₄/NF catalyst achieves a current density of 10&#xa0;mA⋅cm⁻² at a low overpotential of 1.22&#xa0;V vs. reversible hydrogen electrode (RHE). It delivers a remarkable glycerol conversion rate of 90.4% with a formate Faradaic efficiency of 94.3% at 1.35&#xa0;V vs. RHE. Furthermore, the catalyst exhibits excellent long-term electrochemical durability with sustained catalytic performance during extended operation. This work offers a promising strategy to boost the electrocatalytic activity of NiCo₂O₄ through Cu doping, providing new insights into the design of efficient GOR electrocatalysts and contributing to the high-value utilization of biomass-derived molecules and the advancement of green electrochemical energy technologies.</p> Graphical Abstract <p></p>