In this work, laminated ammonium perchlorate-based composite (LAPC) with high thermal decomposition performance was prepared by ice-template freezing-induced assembly strategy. Cobalt-Konjac glucomannan (Co2+-KGM) hydrosol with rich AP embedded was designed and used as a frozen precursor. LAPC was obtained from the ice-template freezing of the hydrosol precursor and crystallization of AP molecules. The structure and morphology of as-obtained composite were characterized, and the thermal decomposition performances were investigated. The results showed that LAPC materials have micro-/nano-lamellar structures with the thickness size of 20 mu m, which are composed of AP micro-/nanoparticles formed in the freezing crystalline progress and uniformly dispersed Co2+-KGM coated on the surface and inside of the micro-/nanoparticles. Thermal analysis results show that LAPC-2 has a lower decomposition temperature than raw AP, which have decreased by 114.3 degrees C. The activation energy of LAPC-2 thermal decomposition was reduced by 87 kJ/mol from 200 kJ/mol of AP to 113 kJ/mol of LAPC-2. A possible catalytic mechanism of thermal decomposition of LAPC is proposed. Under heating condition, the Co2+-KGM molecules firstly decomposed, and Co-based oxides can be in situ generated on the surface and inside of AP particles, resulting in enhancing the catalytic contact areas. Abundant distributed nanoscale Co-based oxides boosted the thermal decomposition of AP and exhibited excellent catalytic performances.