The effect of Cobalt Fischer-Tropsch catalyst on the thermal degradation of cis-1,4 polybutadiene, polystyrene, chloride) and poly(vinyl acetate) in solution was investigated at various temperatures. The molecular weight distribution of the polymer was obtained by analyzing the samples by gel permeation chromatography. The catalyst enhanced the thermal degradation rate of polybutadiene in solution and had no effect on the thermal degradation of other polymers. However, the catalyst had no effect on the thermal degradation rate of polybutadiene in pyrolysis. Continuous distribution kinetics was used to evaluate the degradation rate coefficients for the thermal and catalytic degradation of polymers in solution. The activation energies, calculated from the temperature dependence of rate coefficients, were 130 kJ/mol and 108 kJ/mol for the thermal and catalytic degradation of polybutadiene in solution, respectively. The Friedman plot was used to determine the activation energy for the degradation of polybutadiene in pyrolysis. © 2004 Elsevier Ltd. All rights reserved.