The preparation of active food packaging materials with both high gas barrier and antioxidant properties remains a great challenge. Hemicellulose is an abundant raw material with excellent oxygen barrier performance and biodegradability, and tea polyphenols (TPs) are natural antioxidants with the function of reducing water sensitivity of polysaccharide-based films. Herein, a synergistic strategy is reported for the preparation of active-controlled food packaging material by incorporating TP into the poly(vinyl alcohol) hemicellulose (PVA/HC) matrix. The obtained film with 5 wt% addition of TP exhibited the highest tensile strength of 41.09 MPa, which was increased by 84% than that of the PVA/HC film. Meanwhile, water vapor permeability was decreased by 25% to 7.39 × 10⁻¹² g⋅cm/(cm²⋅s⋅Pa) compared to a PVA/HC film. Moreover, the addition of TP improved the thermal stability of the (PVA/HC/TP)_n film. The outstanding packaging performances were attributed to the robust hydrogen bonding between TP and the PVA/HC matrix as demonstrated by Fourier transform infrared spectroscopy. The DPPH free radical scavenging of (PVA/HC/TP)₁₅ films reached 87.99%, and the film also exhibited enhanced inhibition efficiency against the microorganism E. coli. Compared with the polyethylene plastic wrap, the film showed excellent food packaging applicability by preventing air oxidation of fresh-cut potato. This study sheds light on a design strategy for active packaging films using a natural substance and easily available biomass.