Flexible composite films of $V_2O_5$ and conductive polypyrrole ($V_2O_5$/PPy) were grown by facile electrochemical polymerization, wherein an anodization potential was applied to the substrate electrode in an electrolyte solution containing pyrrole monomer and dispersed $V_2O_5$ particles. The coating of polypyrrole (PPy) on the surface of $V_2O_5$ particles was induced by the oxidative catalytic action of $V_2O_5$ during the electrochemical polymerization of pyrrole. PPy in the composite film connects the isolated $V_2O_5$ particles. This results in the formation of conductive networks in the composite film cathode, thereby enhancing the Li+ ion diffusion to the surface of the isolated $V_2O_5$ particles and thus increasing the accessibility of the $Li^+$ ions. The specific capacity tests of the Li rechargeable batteries revealed that the discharge capacity of this composite film cathode was higher, i.e., $497;mAhg^{-1}$, than that of $V_2O_5$/PPy powder or pristine $V_2O_5$.