V–Al thin films were prepared by DC magnetron sputtering. The dependences of the superconducting transition temperature(Tc) were studied on the composition of the films and on the deposition temperature(Td). A maximum Tc midpoint of 13.0K was obtained for the film with the Al content of 18.5at% prepared at Td of 600°C on glazed alumina substrate. Effects of substrate surfaces on the formation of A15 V3Al were studied. Three different surfaces of non-, Ag- and Au-coated sapphire substrates were prepared. Values of Tc and phases of the films changed significantly with the difference of the coating material. It was found that gold has great effects on suppressing the formation of stable bcc phase and on stabilizing the formation of the metastable A15 phase.