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In this work, the as-cast directionally solidified (DS) Fe–B alloys with various Si contents and different boride orientation were designed and fabricated, and the as-cast microstructures and static oxidation behaviors of the DS Fe–B alloys were investigated extensively. The as-cast microstructure of the DS Fe–B alloys consists of the well-oriented Fe₂B columnar grains and α-Fe, which are strongly refined by Si addition. The oxidation interface of the scales in the DS Fe–B alloy with 3.50 wt.% Si demonstrates an obvious saw-tooth shaped structure and is embedded into the alternating distributed columnar layer structures of the DS Fe–B alloy with oriented Fe₂B and α-Fe matrix, which is beneficial to improve the anti-peeling performance of the oxide film compared with lower amounts of Si addition in DS Fe–B alloys with oriented Fe₂B [002] orientation parallel to the oxidation direction (i.e., oxidation diffusion direction, labeled as Fe₂B_// sample). In the DS Fe–B alloys with oriented Fe₂B [002] orientation vertical to the oxidation direction (i.e., labeled as Fe₂B_⊥ sample), due to the blocking and barrier effect of laminated-structure boride, Si is mainly enriched in the lower part of the oxide film to form a dense SiO₂ thin layer adhered to layered boride. As a result, the internal SiO₂ thin layer plays an obstructed and shielded role in oxidation of the substrate, which hinders the further internal diffusion of oxygen ions and improves the anti-oxidation performance of the Fe₂B_⊥ sample, making the average anti-oxidation performance better than that of the Fe₂B_// sample.