Catalytic activity of cuprous oxide (Cu2O) micro-particles with cubic, octahedral, truncated-octahedral and hollow opened sphere structures for thermal decomposition of ammonium perchlorate (AP) was investigated in this paper. Cu2O with different morphologies were synthesized through one-pot hydrothermal method, which is based on the reduction of Cu(II) with D-(+)-glucose in an alkalic solvent. Morphology, crystal structure and specific surface area of final samples were characterized by using SEM, XRD, and BET, respectively. TG/DTA results show that the samples with different morphologies exhibit quite different catalytic activity in different stage of thermal decomposition of AP. Through comparing them, Cu2O micro-octahedrons with {1 1 1} facets show better catalytic effect than cubes with only {100} facets, while the Cu2O hollow microspheres enhance the high-temperature exothermic decomposition of AP significantly. The authors also discussed some underlying catalytic mechanism and offered some selection basis of catalysts in the thermal decomposition of AP. (C) 2011 Elsevier B.V. All rights reserved.