As a potential material for food packaging, fully biodegradable composite films based on novel functionalized natural polyphenol/Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) were successfully fabricated by solution casting, and also the functionalized natural polyphenol (C18TAx) was synthesized by grafting fatty acid onto natural polyphenol Tannic Acid (TA). The resultant C18TAx with better hydrophobicity was uniformly dispersed into a PHBV matrix. The influence of C18TAx dosage on the mechanical behavior, crystallization behavior and thermal properties of the C18TAx/PHBV composite films was investigated by uniaxial tensile mechanical testing, Differential Scanning Calorimeter (DSC), Polarizing Optical Microscope (POM) and Wide Angle X-ray Diffractometry (WAXD). The results revealed that the x value was about 0.09, showing that about 11/20 phenol hydroxy groups in TA molecules were replaced with fatty acid chains. Compared with those of neat PHBV, the tensile strength and elongation at break of the C18TA0.09/PHBV composite films with 10 wt.% C18TA0.09 content were enhanced by 121%, and 458%, respectively. This improvement was primarily ascribed to intermolecular hydrogen bonding interactions in composite films. This new type of fully biodegradable bio-based composite films shows great potential for food packaging.