The effect of active chemical elements of metal-working lubricants on both the electronic structure and the character of the interatomic bonds of near boundary areas of grains and their fragments is studied using spin-polarized band structure calculations within the LAPW method with the generalized gradient approximation (GGA) of the electron density. The weakest interatomic bonds within the metal bulk are formed in accumulation places of phosphorus, sulphur and chlorine atoms in the boundary areas of grains and their fragments, which penetrate into the surface layers of iron from the metal-working lubricants. These areas are the most predisposed to local plastic deformation of the metal. The lowest shear resistance of atoms occurs in the accumulation places of chlorine atoms, the greatest one–in the accumulation places of phosphorus atoms. The intense local plastic deformation of the metal in the places of accumulation of chlorine atoms can result in formation of the metastable atomic clusters Fe—C—O. These clusters and neigh bouring iron atoms are separated by areas with the low electron density. This leads to a limited participation of valence electrons in the formation of bonds between them and to a relatively easy shift of the structural fragments along the boundaries formed by these clusters. Therefore, the concentration of atomic clusters Fe—O—C in the boundaries of grains and their fragments may contribute to forming the near-surface areas of increased ductility of the material.