Si film electrodes for Li micro-film batteries were fabricated on a Cu substrate and a Ni/Cu film. In the structural properties, Si film had an amorphous structure, while the crystallinity of Ni buffer film was improved after annealing. FE-SEM observation demonstrated differences in surface morphologies of Si films fabricated with different methods. In the electrochemical properties, the Ni-inserted film showed the largest initial charge and discharge capacity, and the cell with annealed Si/Ni/Cu film showed good cycleability. It is believed that the insertion of Ni film as a buffer film improved the charge and discharge capacity owing to the enhancement of adhesion between Si film and Cu substrate.