An advanced heat-resistant hyperbranched poly(phenylene sulfide) (HPPS) had been subjected to dynamic thermogravimetric analysis (TGA) in nitrogen. The presence of a single peak in the DTG cures suggested that weight loss occurs in a single stage. The thermal decomposition kinetics had been analyzed by applying the Kissinger, Friedman and Ozawa-Flynn methods. The E values determined for the hyperbranched PPS using these analyses were found to be 183.1, 189.2, 193.9 kJ mol (1), respectively. Coats-Redfern method was used to discuss the probable degradation mechanisms. The solid-state decomposition mechanism followed by the degradation stage of HPPS was Phase boundary controlled mechanism (c) 2008 Wiley, Periodicals, Inc. J Appl Polym Sci 111: 1900-1904, 2009