Structural changes attending polyacrylonitrile(PAN) upon heating and treating with nucleophilic reagents have been studied for some time and a few authors have studied on the thermal degradation, particularly on the characterization of degradation products in PAN. It is the purpose of this paper to report the kinetic study on the thermal degradation above $250^{circ}C$ and make some suggestions as to the degradation process and mechanism in PAN. The degradation process in PAN is considered that three reactions are combined in two steps. Random chain scission accompanying the naphthylidine-type ring formation is the first step and the degradation of naphthylidine-type ring occurred as the next step. The reactions in the first step are competitive so that the maximum weight loss on pyrolysis of PAN, under such a condition that the degradation of naphthylidine-type ring is negligible, is depended on the relative reaction rate of these two competitive reactions.