Orthorhombic structural perovskite NdCrO3 nanocrystals with size of 60 nm were prepared by microemulsion method, and characterized by XRD, TEM, HRTEM, SEM, EDS and BET. The catalytic effect of the NdCrO3 for thermal decomposition of ammonium perchlorate (AP) was investigated by DSC and TG-MS. The results revealed that the NdCrO3 nanoparticles had effective catalysis on the thermal decomposition of AP. Adding 2% of NdCrO3 nanoparticles to AP decreased the temperature of thermal decomposition by 87° and increased the heat of decomposition from 590 to 1073 J g−1. Gaseous products of thermal decomposition of AP were NH3, H2O, O2, HCl, N2O, NO, NO2 and Cl2. The mechanism of catalytic action was based on the presence of superoxide ion O2− on the surface of NdCrO3, and the difference of thermal decomposition of AP with 2% of NdCrO3 and pure AP was mainly caused by the different extent of oxidation of ammonium.