Based on the empirical electronic theory of solids and molecules (EET),the actual model for unit cell of cementite (θ-Fe3C) was built and the valence electron structures (VES) of cementite with specified site and a number of Fe atoms substituted by alloying atoms ofM (M=Cr,V,W,Mo,Mn) were computed by statistical method.By defining P as the stability factor,the stability of alloyed cementite with different numbers and sites of Fe atoms substituted by M was calculated.Calculation results show that the density of lattice electrons,the symmetry of distribution of covalent electron pairs and bond energy have huge influence on the stability of alloyed cementite.It is more stable as M substitutes for Fe2 than for Fe1.The alloyed cementite is the most stable when Cr,Mo,W and V substitute for 2 atoms of Fe2 at the sites of Nos.2 and 3 (or No.6 and No.7).The stability of alloyed cementite decreases gradually as being substitutional doped by W,Cr,V,Mo and Mn.