The work aims to modify the polyvinyl alcohol (PVA) with different water-soluble and fat-soluble antioxidants in order to improve the antioxidant properties of the composite film on the basis of enhancing its comprehensive performance. With tea polyphenols, citric acid, BHT and vitamin E as variables and glycerol/polyvinyl alcohol as basis, the effects of different water-soluble and fat-soluble antioxidants on the morphology, mechanical properties, light transmittance, water resistance and antioxidant capacity of the composite film were studied. The properties of the films were enhanced by adding proper amount of antioxidant. The mechanical properties of tea polyphenols/polyvinyl alcohol composite film were the best. The tensile strength of tea polyphenols (1.5%)/PVA composite film could reach 47.85 MPa and the breaking elongation rate was up to 375.69%. The composite film could significantly improve the UV absorption rate, and the free radical scavenging rate of 73.93% was the highest among all the studied films. Using tea polyphenol to modify polyvinyl alcohol can not only improve the packaging strength of composite film and enhance its water resistance, but also strengthen its antioxidant and antibacterial properties, providing a good idea for food preservation.