Porous metals are recently gaining interest in various fields with lots of advantages of high conductivity, high surface area, good permeability and light weight properties. In present study, a novel three-dimensional porous nickel films (3DNFs) have been efficiently fabricated by controllable electrodeposition of Ni micro-particles using hydrogen bubbles as the template at ambient temperature and pressure. The morphologies and microstructures of products were analyze by field emission scanning electron microscopy (FESEM) and X-ray powder diffraction (XRD), respectively. The formation mechanism of 3DNFs was firstly explored by time sequential experiments. In addition, electrochemical measurements indicate that the obtained 3DNFs possess great electrocatalytic properties for methanol and ethanol oxidation reaction due to the high surface area and outstanding open porous structures. Thus, the great cycle life and catalytic properties of product indicate the great prospect of the promising catalyst with wide applications in catalysis, sensors and purification.