Pulsed-IR laser-induced decomposition of poly-(vinyl acetate) (PVAC) differs remarkably from its conventional pyrolysis, which results in the formation of acetic acid and non-polar carbonaceous residue. In contrast, the products in the former case are (i) vinyl acetate (low energy channel), (ii) products of cleavage in the acetate group, and (iii) an ablatively deposited polar polymeric film containing roughly half of the acetoxy groups initially present.