An en viron mentally friendly phenolic resin/Al2O3 hybrid composite was prepared. Al2O3 particles were pretreated with a silcane coupling agent, then the mixture of paraformaldehyde and treated Al2O3 was grinded with ball crusher for several hours, and added during the phenolic resin polymerization process, finally got the hybrid composite. The kinetic parameters of thermal degradation were calculated by the methods of Kissinger, Flynn-Wall-Ozawa and Crane. The thermal degradation activation energy of environmentally friendly phenolic resin/Al2O3 hybrid composite is approximate three times of pure phenolic resin. The results show that the heat resistance is obviously improved. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 3675-3679, 2010