The effects of RE, V, Ti and B on the microstructure and properties of high chromium cast iron containing 3% molybdenum under as-cast and heat treatment conditions were investigated with the method of comparing experiments. The results show that with the increase of RE content, the primary austenite of high chromium east iron is obviously refined. The morphology of carbide is changed from netlike and lath to small multiangular isolated blocks or massive blocks, the isolated degree of carbide is improved obviously, and the size is significantly re-fined. The addition of V and B into high chromium cast iron can refine the microstructure, reduce coarse columnar crystals and make the carbide smaller and uniform. Through composite modification with RE, V, Ti and B, the hardness, wear resistance and impact toughness of high chromium cast iron are increased conspicuously. After heat treatment, the hardness of high chromium iron is increased significantly, but the toughness and wear resistance do not show great improvement.