In order to study the catalytic performance of bimetallic oxides in solid propellants, the honeycombs ZnCo₂O₄（ZnCo₂O₄(HCs)） particles grown on nickel foam (NF) were successfully prepared by solvothermal method and the subsequent thermal annealing process. Its phase composition and morphology structure were systematically characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopic(FT-IR), scanning electron microscopy (SEM) and N₂ adsorption-desorption test. The thermal behavior of ammonium perchlorate (AP) and hexanitrohexaazaisowurtzane (CL-20) catalyzed by ZnCo₂O₄(HCs) were investigated by differential scanning calorimetry (DSC). Results showed that when 20% ZnCo₂O₄(HCs) is added, the thermal decomposition peak temperatures of ZnCo₂O₄(HCs)/AP and ZnCo₂O₄(HCs)/CL-20 decreased most which were 575.01 K and 521.55 K, respectively. Compared with pure AP and CL-20, the exothermic decomposition peak temperatures of ZnCo₂O₄(HCs)/AP and ZnCo₂O₄(HCs)/CL-20 were decreased by 101.87 and 3.73 K and the apparent activation energies calculated by thermal analysis kinetics were reduced by 17.88 and 6.23 kJ·mol^-1. Furthermore, the as-prepared ZnCo₂O₄(HCs) exhibited good catalytic activity comparing with ZnCo₂O₄ nanocrystallites (NCs), nanowires (NWs) and nanospheres (NSs). This can be attributed to the porous structure and large specific surface area of ZnCo₂O₄(HCs), which can provide rich active sites as a catalyst for the thermal decomposition reaction.