The effect of manganese on the as-cast structure and hardening behavior of high chromium white cast iron subjected to sub-critical treatment was studied. The results indicate that the fraction of retained austenite and the manganese distribution in as-cast alloys are controlled by manganese content. The manganese distribution in as-cast alloys is not homogeneous. The manganese content in carbide is higher than that in matrix. Whether the secondary hardening occurs or not and the peak hardness of secondary hardening is controlled by manganese content in retained austenite in as-cast structure. Higher manganese content can cause more retained austenite. The secondary hardening occurs in sub-critical treating process if the fraction of retained austenite is high.