Two reaction schemes were developed to covalently graft poly(ethylene glycol) (PEG) chains on poly(ethylene-co-acrylic acid) (EAA) surfaces. The schemes involved surface grafting of linker molecules L-lysine or polypropyleneamine dendrimer (AM64), with subsequent covalent bonding of PEG chains to the linker molecules. NHS and EDC were used to activate the carboxylic acid groups of the EAA in the outermost region of the film, estimated to be 20 nm by ATR-FTIR spectroscopy. XPS demonstrated that the conversion of this activation step was almost 100% in the detected region. After activation, L-lysine or dendrimer was grafted onto the EAA surface, followed by PEG grafting. Combining the data from ATR-FTIR, XPS, and contact angle goniometry, it was found that the PEG chains were grafted on the surface of the EAA film and larger surface coverage was achieved when the dendrimer was used as the intermediate layer. This surface also had the lowest water contact angle.