The freckle formation and their phase characterization in freckle areas were investigated by means of microstructure analysis approaches and a thermodynamic equilibrium phase calculation method in a Ni-Cr-Mo-Fe-W alloy. These results show that in freckle areas a large number of M6C, μ and P phases precipitate in grain boundaries even within grain due to the enrichment and segregation of Mo and C during solidification, which results in small grains in freckle areas. Equilibrium phase and liquid segregation calculation can give an reasonable interpretation of the freckle feature for this alloy. The freckle formation and their phase characterization in freckle areas were investigated by means of microstructure analysis approaches and a thermodynamic equilibrium phase calculation method in a Ni-Cr-Mo-Fe-W alloy. These results show that in freckle areas a large number of M6C , μ and P phases precipitate in grain boundaries even within grain due to the enrichment and segregation of Mo and C during solidification, which results in small grains in freckle areas. Equilibrium phase and liquid segregation calculation can give an reasonable interpretation of the freckle feature for this alloy.