Composite powders combining boron with BiF3 and Bi in different amounts were prepared by high energy milling. Thermal analysis in an argon-oxygen mixture showed significant oxidation starting about 200 K lower than for pure boron. Selective oxidation of metallic Bi at low temperatures was observed. Composites containing either Bi or BiF3 ignited more readily than pure boron when heated by a CO2 laser beam. The composites containing BiF3 ignited more readily than boron when in contact with a hot wire. Burn times of particles aerosolized in air and ignited using the CO2 laser were measured as durations of the recorded emission pulses produced by burning particles. Statistical distributions of the measured burn times were correlated with the respective powder's particle size distributions. Compared to elemental boron, burn times of all prepared composites were shorter, including those containing only 10 wt.% of BiF3 or ca. 8 wt.% of Bi, and for most composites combustion temperatures were higher.