Under normal forging and annealing conditions, there are different ultra fine carbides (M3C, M23C6, M7C3, M6C and MC) in high carbon alloy steels when alloy composition design is carried out properly. On the basis of carbides transformation orderliness, the alloy composition design of the high carbon alloy steels is conducted by phase-equilibrium thermodynamic calculation for Fe-Cr-W-Mo-V-C system. The nucleation and growth of new carbides, dissolution of previous partial carbides in these steels during annealing process, all these lead to ultra-fine distribution of carbides. Due to different crystal structures of carbides and different thermodynamics as well dynamics parameters of the carbides dissolution and precipitation, the range of quenching temperature of these steels is widened, and the good temper-resistance is obtained. The characteristics of heat treatment process and microstructure variance, and the carbides transformation for different temperature are explained by the phase-equilibrium component satisfactorily. Their bend and yield strength,flexibility and toughness all are advanced markedly comparing with that of kindred steels. Results of the applications have proved that the microstructure of ultra-fine carbides in these steels played importance roles in the enhancement of edginess and fatigue crack resistance of the die and knives.