Grain refinement is the effective path to simultaneous enhancing both strength and toughness of the metal materials. Here we reported that, a super grain refinement effect has been acquired in the as-cast FeCoCrNiMn high entropy alloy via adding into 0.19 wt% B. The grain size distribution has been mainly concentrated below 150 µm and the average grain size has been refined from 3903 µm to 80 µm after B adding. The electron microscopy characterizations and relevant model calculations indicates that the B can form Cr2B phase which can be used as a high-efficiency nucleating agent and significantly refine the grain of the high entropy alloy. Meanwhile, the orientation relationships between the Cr2B phase and the HEA matrix have been confirmed.