In this paper we describe a two-step surface modification process of poly(ethylene-co-vinyl alc.) by exploiting hexachlorocyclophosphazene and poly(dichlorophosphazene) as coupling agents. Part of the P-Cl groups of the chlorophosphazenes is first reacted with the surface hydroxylic groups of the substrate to form covalent P-O-C bonds, the remaining being utilized for successive substitution reactions with different nucleophiles (i.e. 2,2,2-trifluoroethanol, heptadecafluorononanol and 4-hydroxyazobenzene). Modified surface properties, such as hydrophobicity improvement with fluorinated alcs. and photochromic features with the azobenzene deriv., were verified by contact angle measurements and UV-Vis spectroscopy, resp., while changes in surface compn. were demonstrated through XPS spectroscopy.