Given that tree extracts such as tannin and lignin can be efficiently used as modifying materials, this helps to verify the global trend of energy saving and environment protection. Thus, bio-based biodegradable composite film incorporating tannin and lignin as additives, together with polyvinyl alcohol (PVOH) as a matrix (denoted TLP), was prepared. Its easy preparation process endows it with high industrial value in comparison to some bio-based films with complex preparation process such as cellulose-based films. Furthermore, imaging with scanning electron microscopy (SEM) shows that the surface of tannin- and lignin-modified polyvinyl alcohol film was smooth, free of pores or cracks. Moreover, the addition of lignin and tannin improved the tensile strength of the film, which reached 31.3 MPa as indicated by mechanical characterization. This was accounted for by using Fourier transform infrared (FTIR) and electrospray ionization mass (ESI-MS) spectroscopy, which showed that the physical blending of lignin and tannin with PVOH was accompanied by chemical interactions that gave rise to weakening of the prevailing hydrogen bonding in PVOH film. In consequence, the addition of tannin and lignin acquired the composite film good resistance against the light in the ultraviolet and visible range (UV-_VL). Furthermore, the film exhibited biodegradability with a mass loss about 4.22% when contaminated with Penicillium sp. for 12 days.