High-entropy alloys have raised great interest in recent years because of their potential applications for multi-electron reactions owing to their diverse active sites and multielement tunability. However, the difficulty of synthesis is an obstacle to their development due to phase separation often exists. In addition, it’s a challenge to precisely control morphology in harsh conditions, thus leading to nanoparticles in many cases. We report a facile method to obtain PdPtPbSnNi HEA NWs by solvothermal synthesis method that no existing phase separation. PdPb nucleation plays a role in the formation of the high-entropy structure that serves as a PdPb nucleus for Sn, Ni, and Pt reduction subsequently, thus forming a single phase and an orderly-arranged nanowire structure. Significantly, the optimized PdPtPbSnNi NWs exhibit excellent catalytic activity and stability for both EOR and MOR which is 4.36 A mgPd+Pt-1 and 4.34 A mgPd+Pt-1, respectively. This study highlights a novel strategy for morphology tuning, providing a prospect for designing superior high-entropy nano-catalysts for multi-step reactions.