Si thin films were deposited directly on stainless steel substrates that act as current collectors using the pulsed laser deposition (PLD) technique. Amorphous Si films of different thicknesses were obtained at the Ar gas pressure of 5×10−5 Torr and a temperature of 500°C but different deposition times. The microstructure and morphology of the films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and atomic force microscopy (AFM). The anodic electrochemical performance of the films was examined in the range of 0.005–1.5V, which revealed excellent cyclic stability without any large capacity fade up to the 70th cycle. The PLD process was suitable for improving the density and adhesion behavior of the films.