Proton-exchange membrane fuel cells are considered as promising energy-conversion devices. Alloying 3d transition metals with noble metals not only highly improves the performance of noble metal-based catalysts towards electrocatalytic reactions in fuel cells due to d-d hybridization interaction but also decreases the total cost. However, the rapid leaching of transition metal atoms leads to a fast decay of the activity, which seriously affects the performance of the fuel cell. Herein, alloyed Pd-main group metal (e.g. Pb, Bi, Sn) ultrathin nanowires were realized by a facile one-step wet-chemical strategy. The content of the main group metal could be tuned in a certain range while maintaining the same one-dimensional ultrathin nanowire morphology, which provided a large surface area and many more active sites. These Pd-based alloys showed a significant improvement in electrocatalytic activity and durability towards the oxygen reaction reaction as well as ethanol oxidation reaction. Optimal activity occurred when a small amount of main group metal existed, which could be explained through calculations by a strong p-d hybridization interaction between the main group metal and Pd to optimize the surface electronic structure collaboratively. Besides, high stability was achieved, which could be ascribed to the increased antioxidant activity of Pd by the main group metal. Furthermore, the low amount of the main group metal atoms also prevented them from leaching out of the crystal lattice.