Ultrathin RhCuAgPd/Pd nanowire heterostructures were prepared by a seed-mediated growth method. Due to the synergistic structural (including ultrathin NWs and interfaces) and compositional (Pd, Rh, Cu and Ag) advantages, the RhCuAgPd/Pd NWs exhibit superior electrocatalytic performance toward ethylene glycol oxidation under alkaline conditions, including high mass activity (6.63 A mg_Pd⁻¹), fine stability/durability and resistance to CO poisoning, favourable electrocatalytic kinetics and low activation energy values (18.64 kJ mol⁻¹).