AbstractSulfonation degree determination of sulfonated polystyrene and the corresponding ionomers are performed by adiabatic bomb calorimeter. The theoretical calculations from the band energies for the combustion enthalpy values (calorific values) and the experimental values are compared, and a linear relation between the values is found. Sulfonation and neutralization processes are examined by elemental sulfur analysis and atomic absorption spectroscopy (AAS). It was obvious that increasing sulfonation degree yields a decrease in the combustion enthalpy values, as it is expected from the theoretical calculations. In addition, metal ion incorporation to the structure deviates the experimental combustion enthalpy values especially for the ionomers which have higher sulfonation degrees. This is due to the formation of a higher degree aggregation. © Wiley Periodicals, Inc. J Appl Polym Sci 100: 4684–4688, 2006