In this study, we reported PVA nanocomposite films enhanced by polyethyleneimine (PEI)-lignin contained cellulose nanofibers (LCNFs) via the solvent casting method. An easy and available method was preformed to prepare LCNFs using a supermasscolloider from unbleached bamboo waste after a mild alkaline pretreatment. The results demonstrate that LCNF-PEI can greatly improve mechanical, hydrophobic, anti-UV shielding and antibacterial properties of the composite films. The tensile strength of LPP1 film was improved to 54.56 MPa, which was higher than 39.37 MPa of PVA film. The water contact angle of films increased from 35° to 104° with an increase in LCNF content from 0 to 6 wt%. Meanwhile, the nanocomposite film demonstrated the effect of full shielding against ultraviolet light when the amount of LCNF-PEI reached 6 wt%. The addition of LCNF-PEI endowed excellent antibacterial activity (against S. aureus and E. coli), which indicated potential applications in the packaging field.