The pursuit of high combustion performance and good mechanical properties is an urgent need for the development of composite solid propellants. Ammonium perchlorate/cobalt alginate/ZIF-67 (AP/Co-A/ZIF) composites were successfully synthesized by droplet and solution assembly method. The layered porous structure of Co-A increases the reaction site between AP and ZIF-67 so that is oxidized to produce Co3O4 earlier, and further accelerate the heat release of the system. carbonized porous framework formed by the decomposition of Co-A has kind electrical and thermal conductivity, and makes Co3O4 produced by the decomposition of ZIF-67 and Co-A well dispersed on the framework, achieving efficient charge transfer. The synergistic catalysis of Co-A/ZIF makes the low and high temperature decomposition stages of AP combine, which the high temperature decomposition temperature greatly reduced with a higher heat release. After being applied to AP-based propellants, the organic porous structure of Co-A shortens the heat transfer distance and plays an obvious combustion-supporting effect, while ZIF-67 accelerates the energy release rate to burn more violently, so that considerably improves the ignition capacity and combustion rate of the propellant. In addition, the reaction of Co-A and TDI effectively strengthens the interface interaction between AP and binder matrix, alleviates the dewetting phenomenon, and enormously improves the mechanical properties of the propellant. As an efficient composite nonmetallic combustion catalyst, Co-A/ZIF not only exhibits strong synergistic catalytic ability for propellant combustion, but also effectively improves the mechanical properties of the propellant. It provides a development direction for building a new catalyst to enhance the comprehensive performance of AP-based solid propellant.