Thermal degradation of conducting polymer composites of polythiophene and rubbers was studied by direct and indirect pyrolysis mass spectrometry techniques. The samples were prepared by electrooxidation of polythiophene using natural rubber or synthetic rubber as the insulating matrix. Presence of decomposition products which were not observed during pyrolysis of pure polythiophene and rubbers, and disappearance of rubber-based pyrolysis mass peaks, together with changes in thermal stability and behaviour, may directly be related to a chemical interaction between the components of the composites. The pyrolysis data were used to propose possible polymerization and degradation mechanisms.