The variations of microstructure and mechanical properties of a high-chromium cast iron for rolls were studied from as-cast to the final heat treatments. Results show that the as-cast microstructure of the HCCI consists of M7C3carbide, M23C6carbide, martensite matrix, and retained austenite. The large dendritic M7C3carbide surrounds the matrix, and the M23C6carbide is mainly distributed in the matrix. Part of M23C6carbide transforms to M7C3carbide and is dissolved in austenite during austenization at 1020°C. Thus, the amount of M23C6carbide decreases, whereas that of M7C3carbide increases after quenching; the highest hardness is also obtained. After tempering, the martensite transforms to a tempered martensite, and some carbide precipitates in the martensite matrix. The hardness also changes from HRC62.1, which corresponds to quenching, to HRC55.2 and HRC56.3, which correspond to once and twice tempering, respectively. However, tempering could improve the impact toughness and wear resistance of the HCCI.