Polypropylene (PP) and Poly(vinyl alcohol) (PVA) both synthetics polymers but one of them biodegradable, were surface modified by vacuum ultraviolet (VUV) irradiation. After VUV irradiation in an inert nitrogen atmosphere, the films were exposed to oxygen gas. The treated films were characterized by water contact angle measurements (WCA), optical profilometry, FTIR-ATR, XPS, UPS and NEXAFS techniques. PP and PVA VUV-treated films reached superhydrophilic conditions (WCAs <10 degrees) in about 30 min of irradiation under our experimental conditions. It was observed that when the WCAs reached about 35-40 the hydrophilicity was permanent in both polymers. These results contrasted with typical plasma treatments were a rapid hydrophobic recovery with aging time is usually observed. UPS and XPS data showed the presence of new functionalities on the PP and PVA surfaces that were assigned to COO, C=O, C-O and C=C functional groups. Finally, grafting of styrene (ST) as a typical monomer was tested on PP films. It was confirmed that only in the VUV irradiated region an efficient grafting of ST or polymerized ST was found. Outside the irradiated regions no ST grafted was observed. Our results showed the potential use of VUV treatment for surface modification and processing of polymers which lack chromophores in the UV region. (C) 2016 Elsevier B.V. All rights reserved.