IR laser-induced modification of poly(vinyl acetate) (PVAC) was examined through ablative and non-ablative thermal processing of bulk PVAC. Both laser-induced processes differ remarkably from conventional heating of PVAC, which yields acetic acid and non-polar carbonaceous residue. The non-ablative treatment at low-fluence irradiations results in the formation of volatile vinyl acetate and acetone and leaves the remaining irradiated polymer having an almost identical structure. The ablative treatment at high-fluence irradiations yields a multitude of volatile compounds (methane, ethane, vinyl acetate, acetone, acetic acid, benzene, H-2, CO and CO2) and affords deposition of thin polymeric films that contain reactive conjugated C=C bonds and half of the initially present acetate groups. Residual reactivity of the C=C bonds leads to polymer crosslinking, substantial decrease in solubility and some increase in thermal stability. The low fluence-induced decomposition stands for the first example of the thermal decomposition of polyvinyls into the monomer and the high-fluence ablative deposition represents a one-step approach to crosslinked (intractable), thermally stable and polar polymeric films from linear-chain polymers with pending functional groups. (c) 2005 Elsevier Ltd. All rights reserved.