Copolymerization of styrene with carbon monoxide to give polyketones (PK) was carried out under homogeneous palladium catalyst and polyaniline (PANI) supported palladium(II) catalyst, respectively. The copolymers were characterized by H-1 NMR, C-13 NMR and GPC. The results indicated that the PK catalyzed by the supported catalyst has narrow molecular weight distribution (PDI = 1.18). For comparison purpose of thermal behaviors of PK prepared by the homogeneous and the supported catalyst, thermogravimetric (TG) analysis and derivative thermogravimetric (DTG) were conducted at different heating rates. The peak temperatures (396-402 degrees C) for PK prepared by the supported catalyst are higher than those (387-395 degrees C) of PK prepared by the homogeneous catalyst. The degradation activation energy (E-k) values were estimated by Flynn-Wall-Ozawa method and Kissinger method, respectively. The E-k values, as determined by two methods, were found to be in the range 270.72 +/- 0.03-297.55 +/- 0.10 kJ mo1(-1). Structures analysis and thermal degradation analysis revealed that the supported catalyst changed the microstructures of PK, resulting in improving thermal stability of PK. Crown Copyright (C) 2014 Published by Elsevier B.V. All rights reserved.