The influence of boron concentration on corrosion resistance of high boron white cast iron dipped into a pure liquid zinc bath at 460°C was investigated. The results reveal that high boron white cast iron containing 3.5 wt.%B exhibits excellent corrosion resistance due to the dense continuous netlike or parallel Fe2B phase which hinders the Fe/Zn interface reaction. The corrosion rate decreases significantly when the boron concentration increases, but the corrosion rate declines slightly when the boron concentration exceeds 3.5wt.%. EDS results indicate the coarse and compact δ phase generated near the matrix and a large amount of massive and blocky phase occurred close to the liquid zinc. The corrosion process includes Fe/Zn interface reaction and the spalling and fracture of Fe2B. The failure of Fe2B is mainly caused by the microcrack of phase transformation.