To investigate the effect of iron on the ignition and combustion behavior of boron particles in air， B@Fe and B/Fe composite fuels with different iron contents were prepared by chemical in-situ coating method and mechanical mixing method， respectively. The thermal oxidation properties and ignition combustion characteristics of samples in air were studied through thermogravimetry-differential scanning calorimetry （TG-DSC） analysis and laser ignition combustion experiments. The results show that B@Fe composite fuel exhibits better ignition and combustion performance in air atmosphere， compared with boron fuel and B/Fe composite fuel. As the iron content increases from 0% to 9%， the ignition temperature and exothermic peak temperature of B@Fe composite fuel decrease by 234.3 K and 321.6 K， respectively. When the iron content is ≥6%， B@Fe composite fuel also exhibits secondary oxidation behavior in air. Specifically， the total heat release during the thermal oxidation process of B@Fe-9 increases by 48.7% compared to boron powder. B@Fe composite fuel generates a large amount of gas during laser ignition， which promotes the dispersion of combustion products. The flame height rising rate of B@Fe composite fuel with 9% iron content is 4.7 times that of boron， and the ignition delay time is reduced by about 27.5% compared with boron. Comparing the thermal oxidation and ignition combustion processes of B， B@Fe and B/Fe， an ignition and combustion mechanism of B@Fe composite fuel is proposed.