To improve the electrochemical performance of Si thin film, we have investigated the effect of the addition of Al in the film. The Si–Al thin film were prepared by co-deposition from Si target embedded with Al rods on Cu foil. The atomic ratio of Al in the film is 18.69% estimated by energy-dispersive spectroscopy. The XRD and TEM analysis revealed that the Si–Al thin film was a complete amorphous structure. The electrochemical performance of the Si–Al thin film as anode material for lithium ion battery was investigated by the cyclic voltammetry and charge/discharge tests. The Si–Al thin film delivered a high reversible capacity of 2257.8mAhg−1 and an initial Coulombic efficiency of 85.9% at 0.05C rates. Compared with pure Si thin film with the same thickness, Si–Al thin film showed superior rate capability and cycle performance. And the Li+ diffusion coefficient of Si–Al thin film is much higher than that of Si thin film.