For traditional photocatalyst composite films, the produced hydrogen and carbon dioxide are mixed together, which is not conducive to the direct use of hydrogen. In this study, a novel immobilized Z-scheme V2O5/FeVO4/430-stainless steel foil (V2O5/FeVO4/430-SSF) photocatalyst composite film was constructed. Thereby, the hydrogen and the carbon dioxide can separately generated on both sides of the photocatalytst film and the pure hydrogen can be obtained. The results show that the photocatalyst composite film prepared under optimal conditions has excellent photocatalytic activity in organic pollutant degradation with simultaneous hydrogen production. Under simulated sunlight irradiation for 120 min, the degradation ratio of tetracycline is 77.53% and the hydrogen production amount reaches 370.81 µmol/dm2. It is hoped that this work could provide some guiding suggestions to designing a photocatalyst composite film for efficient photocatalytic degradation of organic pollutants with simultaneous production of pure hydrogen in the future.