To prevent the agglomeration of cobalt ferrite （CoFe₂O₄） nanoparticles and improve their catalytic decomposition performance for Octogen （HMX） and HATO （TKX-50）， graphitic carbon nitride （g-C₃N₄） was applied as CoFe₂O₄ nanoparticles dispersant carrier. The in suit preparation of CoFe₂O₄/g-C₃N₄ binary nanocomposites were achieved through solvothermal method. Corresponding composition， structure morphology and catalytic decomposition performance of CoFe₂O₄/g-C₃N₄ were investigated through X-ray powder diffractometer， scanning electron microscopy， fourier transform infrared spectrometer and differential scanning calorimeter. The results showed that the morphology of CoFe₂O₄/g-C₃N₄ composites is uniform and dense， which reduces the thermal decomposition peak temperature of HMX and TKX-50 by 7.0 ℃ and 41.3 ℃， respectively， and the apparent activation energy by 341.1 kJ·mol^-1 and 21.0 kJ·mol^-1， respectively. Moreover， the introduction of g-C₃N₄ increases the heat release amount. The results of residue analysis showed that the catalytic decomposition of HMX was very complete， while TKX-50 presents incomplete catalytic decomposition， and its residua formed micron bulk mixtures with CoFe₂O₄/g-C₃N₄.