Ni3P–Ni films were deposited on nickel foam substrates by electrodeposition in an aqueous solution. The structure and morphology of the electrodeposited films were characterized using X-ray diffraction (XRD) and scanning electron microscope (SEM). The annealed electrodeposited films consisted of tetragonal structured Ni3P and cubic metal Ni. As anode for lithium ion batteries, the electrochemical properties of the Ni3P–Ni films were investigated by cyclic voltammetry (CV), electrochemical impedance spectrum (EIS) and galvanostatic charge–discharge tests. The electrodeposition time had a significant effect on the electrochemical performances of the films. The Ni3P–Ni film electrodeposited for 20min delivered the initial discharge capacity of 890mAhg−1. Although the irreversible capacity at the first cycle was relative large, the Ni3P–Ni film exhibited good cycling stability and its discharging capacity still maintained 340mAhg−1 after 40 cycles.