Fluorinated alcohols were used as surface modifying agents, through chain transfer mechanism in cationic UV curing of an epoxy system. The fluorinated alcohols were able to induce surface modification already at very low concentration (below 1 wt %). It has been shown that the surface modification depended on the concentration of the fluoroalcohols, on the length of the fluoroalkyl chain, and on the length of the methylene spacer between the fluorinated chain and the OH group. The strong increase on hydrophobicity in the presence of the synthesized fluorinated alcohol, CF3(CF2)(9)(CH2)(10)OH, was attributed to the higher fluorocontent of the chain as well as to a self-organization effect, (c) 2005 Wiley Periodicals, Inc.