A poly(organophosphazene) functionalized with succinic anhydride groups was bonded to the surfaces of poly(vinyl alcohol) and poly(ethylene-co-vinyl alcohol) films. The starting materials and the resultant surfaces were studied by XPS and ATR-i.r. spectroscopies and contact angle measurements. The comparison of XPS results obtained for the two grafted surfaces gave a clear indication of the protonation of the nitrogen atoms in the phosphazene backbone by the hydroxyl groups of the substrates. The extent of this protonation is greater in the case of the hydroxylated copolymer. The variations of the calculated atomic ratio and the deposited layer thickness versus polyphosphazene concentration demonstrated that the grafting yield is higher in the case of poly(vinyl alcohol). The poly(vinyl alcohol) modified surfaces showed a marked decrease in hydrophilic character.