Multi-metallic alloy nanotube arrays are highly favorable for superior electrocatalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, hollow nanotubes, and array nanostructures. Here we firstly prepared the quinary PdNiCoCuFe alloy nanotube arrays (NTAs) by template-assisted electrodeposition method. The inner diameters, wall thicknesses, and lengths of PdNiCoCuFe alloy nanotubes are 300 similar to 400 nm, 150 nm, and 1.8 mu m, respectively. Because of the high specific surface area, hollow nanotube arrays, and synergistic effects of various elements, the quinary PdNiCoCuFe alloy NTAs as efficient electrocatalysts showed superior catalytic activity and long-term cycle stability for methanol electrooxidation. The combination of compositionally and geometrically favorable factors provides a new method to design the novel catalysts with excellent electroactivity and durability. (C) 2014 Elsevier Ltd. All rights reserved.