One of the challenges in solid propellant formulation is the ability to extend the combustion performance by efficiently catalyzing the decomposition of energetic additives. Herein, a series of cobalt acid composites nano-MCo₂O₄ (M = Cu, Ni, Zn, Mg, Fe, Ba) with homogeneous morphology and small particle size were systematically prepared by a solvothermal method. The crystal structure, surface morphology and catalytic performance of MCo₂O₄ were adjusted by the special co-solvent isopropanol and glycerol, exhibiting a regular and uniform spherical structure with an average diameter of 900 nm. The surface of MCo₂O₄ before calcination is wrapped with a layer of a fold-like substance, which is related to the addition of glycerol. XRD results show that BaCo₂O₄ was firstly prepared by this method in this study. Finally, the catalytic decomposition performance of MCo₂O₄ composites toward ammonium perchlorate (AP) and cyclotrimethylenetrinitramine (RDX) was investigated and compared via the DSC method. BaCo₂O₄ and CuCo₂O₄ exhibit the best catalytic activity toward AP and RDX, respectively, which is mainly due to their higher crystallinity and the better catalytic activity of copper ions. The simple and high-yield pathway for obtaining nano-MCo₂O₄ in this work provides a new insight to design and develop a kind of high-performance combustion catalyst for solid propellants.