The effects of Co, Ni together with W addition on the precipitation sequence, amount, and composition of carbides and FCC matrix in Fe–C–V–Cr–Mo based alloys are investigated with the help of Partial Equilibrium (PE) approximation and thermodynamic calculations as well as differential scanning calorimetry (DSC) and electron backscatter diffraction (EBSD) - energy dispersive spectrometer (EDS) analyses. Results show that, individually, Co and Ni elements strengthen the matrix by their great solubility in FCC matrix; W element enlarges the hardness of the alloy through benefiting the formation of M6C carbide. Mutually, the addition of Co and Ni together with W increases the precipitation temperature of the eutectic carbides, although the addition of Co and Ni itself exerts little influence on the nature (type, amount, and composition) of the carbides. These predictions combined with the experimental verifications provide potentials for the alloy design and the property control in high speed steels.