Nanocrystalline CoxZn1-xCr2O4 (x=0.7, 0.8, 0.9, 0.95, and 1) was synthesized by the low-temperature combustion synthesis method using citric acid as reductant and metal nitrates as oxidants. XRD, TEM, FT-IR and DSC were employed to characterize the structure, morphology, infrared curve and the catalytic performance for the ammonium perchlorate (AP) decomposition of the sample, respectively. Results show that cubic spinel-type solid solution of 30 nm CoxZn1-xCr2O4 particles can be obtained at 800 °C. The absorption bands in IR curve at 528 cm-1 and 627 cm-1 corresponding to the vibration of octahedron group [CrO6], the peaks slightly shift to high wave number with the increase of the x value. Compared with the thermal decomposition of pure AP, adding CoxZn1-xCr2O4 nanoparticles in AP decreases its decomposition temperature by 58~68 °C and increases its apparent decomposition heat to 1049.62~740.13 J/g, exhibiting signiﬁcant catalytic effect. Catalytic mechanism is due to the lattice of transition metal ions Co2 + and Cr3 + in the outer d orbital electron transfer, which provides a good space and produces complex with NH3 ligands of ammonium perchlorate’s dissociation products.