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The changes of tempering microstructure and properties of Fe-Cr-V-Ni-Mn-C cast alloys with martensite matrix and much retained austenite are studied. The results showed that when tempering at 200℃ the amount of retained austenite in the alloys is so much that is nearly to as-cast, and a lot of retained austenite decomposes when tempering at 350℃ and the retained austenite decomposes almost until tempering at 560℃. When tempering at 600℃, the retained austenite in the alloys all decomposes. At 560℃ the hardness is highest due to secondary hardening. The effect of nickel and manganese on the microstructure and properties of Fe-Cr-V-C cast alloy were also studied. The results show that the Fe-Cr-V-C cast alloy added nickel and manganese can obtain martensite matrix and much retained austenite microstructure, and nickel can also prevent pearlite transformation. With the increasing content of nickel and manganese, the hardness of as-cast alloy will decreases gradually, so one can improve the hardness of alloy by tempering process. When the content of nickel and manganese is 1.3～1.7%, the hardness of secondary hardening is the highest (HRC64). But when the content of nickel and manganese increase continually, the hardness of secondary hardening is low slightly, and the tempering temperature of secondary hardening rises.