The multilayer films consisting of active (Si) and inactive (Fe) metal elements were investigated as anodes for lithium rechargeable batteries. It has been revealed that the electrochemical performance of as-deposited Fe/Si multilayer films could be improved and optimized by controlling the multilayer structure like the thickness and number of stacked layers as well as post-annealing treatment. It appears that the adhesion between Si film and current collecting substrate is critical for attaining a prolonged cycling stability, which can be effectively achieved by insertion of an adhesion-promoting layer selected based on the chemical affinity between the constituent elements at a given interface. Fe/Si multilayer film electrodes have shown acceptable electrochemical properties as an anode material.