The plasma source ion implantation (PSII) technique was used to improve the adhesion between linear low-density polyethylene (LLDPE) and biopolymer. LLDPE was treated with the PSII using O(2) or CF(4) gas to modify its surface. After modification, chitosan or corn zein was used for coating on LLDPE. Wettability of the LLDPE surface was evaluated with a contact angle meter by the sessile drop method. X-ray photoelectron spectroscopy (XPS) was used to analyze the LLDPE surface. Before and after treatment, in the case of LLDPE treated with O(2) PSII, oxygen-containing functional groups were formed on the implanted surface. In the CF(4) PSII treated LLDPE, it was observed that the fluorine concentration on the surface of LLDPE remarkably increased and hydrophobic groups were formed by chemical reaction. Bilayer films coated with chitosan or corn zein showed 10 times lower oxygen permeability. Tensile strength of multilayer films was decreased a little compared with that of LLDPE. The plastic and biopolymer multilayer films have potential for food packaging application because of their O(2) gas barrier property and easy recyclability of the multilayer film.