Biomass is a sustainable and renewable resource that can be converted into valuable chemicals, reducing the demand for fossil energy. 5-Hydroxymethylfurfural (HMF), as an important biomass platform molecule, can be converted to high-value-added 2,5-furandicarboxylic acid (FDCA) via a green and renewable electrocatalytic oxidation route under mild reaction conditions, but efficient electrocatalysts are still lacking. Herein, we rationally fabricate a novel self-supported electrocatalyst of core-shell-structured copper hydroxide nanowires@cerium-doped nickel hydroxide nanosheets composite nanowires on a copper mesh (CuH_NWs@Ce:NiH_NSs/Cu) for electrocatalytically oxidizing HMF to FDCA. The integrated configuration of composite nanowires with rich interstitial spaces between them facilitates fast mass/electron transfer, improved conductivity, and complete exposure of active sites. The doping of Ce ions in nickel hydroxide nanosheets (NiH_NSs) and the coupling of copper hydroxide nanowires (CuH_NWs) regulate the electronic structure of the Ni active sites and optimize the adsorption strength of the active sites to the reactant, meanwhile promoting the generation of strong oxidation agents of Ni3+ species, thereby resulting in improved electrocatalytic activity. Consequently, the optimal CuH_NWs@Ce:NiH_NSs/Cu electrocatalyst is able to achieve a HMF conversion of 98.5% with a FDCA yield of 97.9% and a Faradaic efficiency of 98.0% at a low constant potential of 1.45 V versus reversible hydrogen electrode. Meanwhile, no activity attenuation can be found after 15 successive cycling tests. Such electrocatalytic performance suppresses most of the reported Cu-based and Ni-based electrocatalysts. This work highlights the importance of structure and doping engineering strategies for the rational fabrication of high-performance electrocatalysts for biomass upgrading.