In this study, the intrinsic brittleness of poly(lactic acid) (PLA) was overcome by chemical modification using ethyl acetate-extracted lignin (EL) via cationic ring-opening polymerization (CROP). The CROP was conducted to promote homopolymerization under starvation of the initiator (oxyrane). This method resulted in the formation of lignin-based polyether (LPE). LPE exhibited enhanced interfacial compatibility with nonpolar and hydrophobic PLA owing to the fewer hydrophilic hydroxyl groups and a long polyether chain. In addition, because of the UV-protecting and radical-scavenging abilities of lignin, LPE/PLA exhibited multifunctional properties, resulting in improved chemical properties compared with the neat PLA film. Notably, one of the LPE/PLA films (EL_MCF) exhibited excellent elongation at break of 297.7 % and toughness of 39.92 MJ/m3. Furthermore, the EL_MCF film showed superior UV-protective properties of 99.52 % in UVA and 88.95 % in UVB ranges, both significantly higher than those of the PLA film, without sacrificing significant transparency in 515 nm. In addition, the radical scavenging activity improved after adding LPE to the PLA film. These results suggest that LPEs can be used as plasticizing additives in LPE/PLA composite films, offering improved physicochemical properties.