The thermal degradation of poly(vinyl sulfonic acid) and its sodium salt, poly(4-styrenesulfonic acid) and its sodium salt, and poly(vinylphosphonic acid) was studied by a combination of techniques, including TGA/FTIR, to identify the volatile products which were evolved during the degradation as well as analysis of the residues which were obtained in order to propose a mechanism for the degradation. The motivation for the work was to attempt to identify new monomers which could be graft copolymerized onto a polymer in order to improve the thermal stability of that polymer