Films of Poly(ethylene oxide), PEO, were modified to impart hydrophilicity via UV irradiation. The UV irradiation treatment produced new photo-oxidized groups of carbonyl and ether groups as indicated in ATR and ESCA analysis. It was found that water contact angle decreased from $15^{circ}C$ to $10^{circ}C$ and total surface energy of PEO increased from 54.2 mN/m to 76.6 mN/m with increasing UV energy, which was attributed to significant contribution of acid base interaction of the photo-oxidized PEO rather than nonpolar interaction originating from the dominant increase in Lewis acid parameter. The increased hydrophilicity and surface energy were also proved by the decreased water wetting time.