Simultaneously achieving electrochemical conversion of biomass-derived molecules into value-added products and energy-efficient hydrogen production is a highly attractive strategy but challenging. Herein, we reported a heterostructured Ni/Ni0.2Mo0.8N nanorod array electrocatalyst deposited on nickel foam (Ni/Ni0.2Mo0.8N/NF), which exhibited excellent electrocatalytic activity toward 5-hydroxymethylfurfural (HMF) oxidation, and nearly 100% conversion of HMF and 98.5% yield of 2,5-furandicarboxylic acid (FDCA) products can be achieved. The post-reaction characterizations unveil that Ni species in Ni/Ni0.2Mo0.8N/NF would be readily converted to NiOOH as the real active sites. Furthermore, a two-electrode electrolyzer was assembled with Ni/Ni0.2Mo0.8N/NF utilized as a bifunctional electrocatalyst for both the cathode and anode, giving rise to a low voltage of 1.51 V to concurrently produce FDCA and H2 at 50 mA cm-2. This work enlightens the significance of regulating redox activities of transition metals via interfacial engineering and constructing heterostructured electrocatalysts toward more efficient energy utilization.