The effects of UV irradiation on iron(III)chloride doped poly(vinyl alcohol) (PVA) films, using a high molar mass polymer, have been studied. It has been found that the polymer is oxidized and crosslinked during UV irradiation. UV/VIS spectra reveal an exponential loss of absorption at = 360 nm, and the refractive index of the PVA:FeCl3 films decreases significantly during UV irradiation (nD = -0.09). The effects of crosslinking have been studied using the sol-gel technique, which revealed high gel contents due to doping and UV-exposure. Photolithographic patterning of doped PVA films using a medium-pressure mercury-vapor UV source has been carried out, leading to good contrast behavior before and after development in aqueous media. A photobleaching effect was observed, therefore the curing of thicker films is feasible. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013