Corn starch/polyvinyl alcohol (PVA) composite films containing different concentrations of tea polyphenols (TP) were fabricated by casting. Scanning electron microscopy and atomic force microscopy images showed that when the TP content was less than 8%, the films were relatively uniform, but with increasing TP concentration, the films became rougher and uneven. Fourier transform infrared, 13C nuclear magnetic resonance, and X‐ray diffraction techniques were used to investigate the interactions between TP, starch, and PVA. The incorporation of TP deepened the color and increased the opacity and solubility of the films. The tensile strength and elongation at break first increased and then decreased with increasing TP content. Furthermore, the addition of TP increased the antioxidant activity of the films, specifically, their ability to scavenge 2,2‐diphenyl‐1‐picrylhydrazyl and 2,2′‐azinobis (3‐ethylberizothiazoline‐6‐sulfonic acid). The addition of TP can effectively enhance the performance of starch composite films and their potential for application in antioxidant food packaging.