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, four composite were named as μBHHc, μBHCe, nBHHc, and nBHCe. 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 μBHHc and μBHCe composite in argon is 9.7 kJ·g-1, and the maximum combustion efficiency in argon is 66.2 %. The maximum calorific value in oxygen is 14.6 kJ·g-1, the maximum combustion efficiency is in oxygen 93.3%, and the oxidation peak temperature is between 750 ℃ and 760 ℃. The maximum calorific value of nBHHc and nBHCe composite in argon is 9.9 kJ·g-1, and the maximum combustion efficiency is in argon 68.9%. The maximum calorific value in oxygen is 14.8 kJ·g-1, the maximum combustion efficiency in oxygen 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 nBHHc composite is the shortest (26 ms), while the mass burning rate is the highest (1.84 g·s-1). The μBHCe 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 of condensed phase combustion products includes 5-10 μm spheres and 10-20 μm flakes.