- The reliability of the circuits in the modern microelectronic devices remains, during last decades, one of the key topics in research and gains an attention for improving the promising candidates for conductors. Improvement of materials for such applications can be obtained by both electronic and compositional optimization. Ab initio calculations using full potential linearized augmented plane wave method in density functional theory are applied to explain the reduction in electromigration effect in the vicinity of grain boundaries (GB) in nano-structured Cu due to the segregation of some additives to the GB. Several possible mechanisms are considered. It is demonstrated that S atoms segregated to GB of nano-structured Cu lead to the growth of effective mass of the electrons. This decreases the mobility of electrons in external electric field, and, correspondingly, the momentum that they may transfer to atoms in collisions. Fe atoms segregated to GB of Cu create new empty states at the top of the valance band. These non-occupied states may stimulate the current of holes when external electric field is applied to the system, creating the “hole wind” in the direction opposite to the current of electrons. Such “hole wind” will compensate the forces generated by the electron current and therefore will reduce the total momentum transfer between charge carriers and atoms. The calculated electron density maps show that S and Fe segregating to Cu GB increases the strength of covalent bonds reducing the diffusion of Cu atoms in the vicinity of GB.