The work aims to prepare PVA composite films by means of montmorillonite (MMT) incorporated with tea polyphenols (TP) as modified agent, expecting to improve comprehensive properties of pure PVA film, so as to replace the traditional packaging film. The solution casting method was used to prepare the PVA/MMT composite films with different mass fractions of TP (the additive amount of MMT was equivalent to 3.0% of PVA mass). The properties of PVA/MMT composite films were analyzed, including water resistance, mechanical properties, water vapor barrier properties and ox-idation resistance. Results showed that, when the mass fraction of TP was 3.0%, the swelling rate and solution weight loss rate were about 532% and 12.3%, respectively, the water vapor permeability coefficient was about 1.0×10−10 g•m/(m2•Pa•s); tensile strength increased by approximately 26% compared to PVA/MMT composite films, but the elongation at break decreased obviously; and the DPPH free radical scavenging rate of PVA/MMT/TP composite films reached 65.5%. Hence, MMT incorporated with TP is an effective method for improving PVA-based composite films.