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The microstructure and oxidation behavior of Fe–B alloys have been investigated. Oxide scale cross-sectional microstructures oxidized at 1073 K for 100 h have been studied. EPMA investigations show that B 2 O 3 –SiO 2 oxides accumulates in the inner oxide layer which improves the oxidation behavior and oxide layer adhesion considerably. Cyclic oxidation kinetics data indicates that Fe–B 3.08 wt.% alloy presents the best oxidation resistance. The formation of diffusion zone in the Fe–B alloys indicate that the oxidation of the Fe 2 B boride is controlled by boron diffusion. The diffusion zone increases with time and reaches a maximum width of 60–65 μm. [ABSTRACT FROM AUTHOR]