A pollen-like porous Fe2O3/Al thermite was prepared by a templated method, with aluminium nanoparticles (Al-NPs) embedded in the porous channels. The thermite prepared by reduced pressure released the largest exothermic heat during DSC testing period compared with Fe2O3/Al thermites prepared by ultrasonic mixing and physical mixing. The exothermic heats in the range of 773 K to 1273 K are 3742.3 Jg(-1), 2279.0 Jg(-1), 1981.1 Jg(-1), and 2621.0 Jg(-1) for pollen-like Fe2O3/Al by reduced pressure, pollen-like Fe2O3/Al by ultrasonic mixing, pollen-like Fe2O3/Al by physical mixing, and commercial Fe2O3/Al by ultrasonic mixing, respectively. The reactivity between Fe2O3 and Al-NPs was efficiently improved, corresponding to its enlarged contact surface area between Al-NPs and the porous pollen-like Fe2O3, and the reduced pre-combustion sintering. Furthermore, pollen-like Fe2O3/Al has good compatibility with both RDX and HMX and it is not compatible with Cl-20 and GAP.