Tempering is an important phenomenon in ferrous alloys. Most steels, especially alloying steels, are used after quenching and tempering. To design the composition of quenching and tempering steels, control the tempering process more effectively, improve the properties after tempering and realize the potentials of steels, the essence of tempering process and the properties of tempering products have to be understood. In this paper, the phase structure factors and interface conjunction factors of common alloying elements in cementite and its interface are calculated out. The relationships between these valence electron structure parameters and (i) the phenomena of martensite decomposition, (ii) transformation, gathering and growth of the carbides and (iii) the mechanical properties of tempering products are buitt up. The nature of the effect of alloying elements on tempering process and properties of tempering products is uncovered on the level of valence electron structure. One new theoretical foundation for alloy design is provided.