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Formic acid (FA) electro-oxidation (FAO) was investigated at a binary catalyst composed of palladium nanoparticles (PdNPs) and copper oxide nanowires (CuOxNWs) and assembled onto a glassy carbon (GC) electrode. /e deposition sequence of PdNPs and CuOxNWs was properly adjusted in such a way that could improve the electrocatalytic activity and stability of the electrode toward FAO. Several techniques including cyclic voltammetry, chronoamperometry, field-emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction were all combined to report the catalyst’s activity and to evaluate its morphology, composition, and structure. /e highest catalytic activity and stability were obtained at the CuOx/Pd/GC electrode (with PdNPs directly deposited onto the GC electrode followed by CuOxNWs with a surface coverage, Γ, of ca. 49%). Such enhancement was inferred from the increase in the peak current of direct FAO (by ca. 1.5 fold) which associated a favorable negative shift in its onset potential (by ca. 30 mV). /e enhanced electrocatalytic activity and stability (decreasing the loss of active material by ca. 1.5-fold) of the CuOx/Pd/GC electrode was believed originating both from facilitating the direct oxidation (decreasing the time needed to oxidize a complete monolayer of FA, increasing turnover frequency, by ca. 2.5-fold) and minimizing the poisoning impact (by ca. 71.5%) at the electrode surface during FAO.