Micrometer-sized cobalt oxalates with different morphologies have been prepared in the presence of surfactants. The effect of catalysts morphology on the thermal decomposition of ammonium perchlorate (AP) was evaluated by differential thermal analysis (DSC). Remarkably, contrary to the well-accepted concepts, no direct relationship between the morphologies of catalysts and their activities has been observed. Based on the structural and morphological variation of the catalysts during the reaction, a catalytic mechanism on thermal decomposition of ammonium perchlorate catalyzed by cobalt oxalate is proposed. We believe that it is the "self-crushing and self-distributed" occurred within the reaction that really works for the improvement of the overall catalytic activities. In this process, both catalysts and reactants have been crashed and distributed uniformly in an automatic way. This work provides an in-depth insight into the thermal decomposition mechanism of AP as catalyzed by oxalates. (C) 2012 Elsevier B.V. All rights reserved.