In order to improve the ignition and combustion performance of boron powder， four kinds of micro- and nano B-Fe-Bi₂O₃@AP/PVDF composite were prepared by high-energy ball milling combined with spray drying method. According to their high calorific value and high combustion efficiency， the four composite were named as μBHH_c， μBHC_e， nBHH_c， and nBHC_e. Their morphology， thermal reactivity， ignition delay time， mass burning rate and condensed phase combustion products were characterized and analyzed. The results show that the maximum calorific value of μBHH_c and μBHC_e composite in argon is 9.7 kJ·g^-1， and the maximum combustion efficiency is 66.2 %. The maximum calorific value in oxygen is 14.6 kJ·g^-1， the maximum combustion efficiency is 93.3%， and the oxidation peak temperature is between 750 ℃ and 760 ℃. The maximum calorific value of nBHH_c and nBHC_e composite in argon is 9.9 kJ·g^-1， and the maximum combustion efficiency is 68.9%. The maximum calorific value in oxygen is 14.8 kJ·g^-1， the maximum combustion efficiency is 97.2%， and the oxidation peak temperature is between 595 ℃ and 600 ℃. The highest combustion temperature of all kinds of composite is between 1954 ℃ and 2011 ℃. The ignition delay time of nBHH_c composite is the shortest （26 ms）， while the mass burning rate is the highest （1.84 g·s^-1）. The μBHC_e composite has the longest ignition delay time （39 ms） and the lowest mass burning rate （0.80 g·s^-1）. The condensed phase combustion products of various composites are mainly composed of B₂O₃， B₄C and a small amount of incompletely burned boron. The morphology includes 5-10 μm spheres and 10-20 μm flakes.