This study presents a novel electrocatalyst, heterostructured PtPd alloy and oxides nanowires (PtPd-ox NWs), for the formate electrooxidation reaction (FOR) in direct formate fuel cells (DFFCs). The catalyst is synthesized using a self-template method, resulting in a 1D nanowire structure with abundant defect sites. The heterostructure between the PtPd alloy and oxides enhances the electronic properties of the catalyst, leading to improved FOR activity and stability. The electronic tuning from the heterojunction influences the work function of PtPd-ox NWs, promoting favorable adsorption of intermediates and strong d-p orbital hybridization between Pt sites and oxygen in formate, which favors the direct FOR pathway with a low energy barrier. Additionally, the heterostructure provides sufficient hydroxyl species to facilitate CO₂ formation, enhancing FOR kinetics. The PtPd-ox NWs exhibit dual regulation of FOR thermodynamics and kinetics, demonstrating remarkable performance and potential for practical applications. The catalyst was tested in DFFCs, showing high open circuit voltage, power density, and stability. The study highlights the importance of alloying and heterojunction design in enhancing FOR performance, and the PtPd-ox NWs show promise for carbon-neutral energy systems by integrating CO₂ capture and utilization with DFFCs.This study presents a novel electrocatalyst, heterostructured PtPd alloy and oxides nanowires (PtPd-ox NWs), for the formate electrooxidation reaction (FOR) in direct formate fuel cells (DFFCs). The catalyst is synthesized using a self-template method, resulting in a 1D nanowire structure with abundant defect sites. The heterostructure between the PtPd alloy and oxides enhances the electronic properties of the catalyst, leading to improved FOR activity and stability. The electronic tuning from the heterojunction influences the work function of PtPd-ox NWs, promoting favorable adsorption of intermediates and strong d-p orbital hybridization between Pt sites and oxygen in formate, which favors the direct FOR pathway with a low energy barrier. Additionally, the heterostructure provides sufficient hydroxyl species to facilitate CO₂ formation, enhancing FOR kinetics. The PtPd-ox NWs exhibit dual regulation of FOR thermodynamics and kinetics, demonstrating remarkable performance and potential for practical applications. The catalyst was tested in DFFCs, showing high open circuit voltage, power density, and stability. The study highlights the importance of alloying and heterojunction design in enhancing FOR performance, and the PtPd-ox NWs show promise for carbon-neutral energy systems by integrating CO₂ capture and utilization with DFFCs.