This paper presents materials on the physico-chemical characteristics of the organization of the structure of surface layer formed by electro-spark processing, as well as the possibilities of this method (ESA) to modify in a wide range the phase composition of the processed surfaces, which in combination provides a high corrosion resistance. It is shown that the increased corrosion resistance of coatings, regardless of alloying electrodes, is associated with the formation of so-called "white layer", in which a high density of dislocations (1015 ÷ 1016 m-2) is formed, which leads to the disordering and breakage of the structure, which is characterized by substructure, distinguished by low density of defects energy [1], the surface energy of which is close to zero. In addition, the nature and specificity of the "white layers" properties are explained by some authors by change of the electronic structure of the metal, the formation of covalent diamond-like structures formed of the elements that make up these layers under the influence of pulsed high temperatures and pressures, as well as alloying elements [2]. Thus, in the iron-carbon alloys, the relationship of carbon atoms in the white layer is very high, which leads to its thermodynamic passivity and, respectively, to low electrochemical (corrosion) activity. The paper also presents the results of studies of corrosion and electrochemical behavior of titanium, copper and iron at the surface modification of their phase composition. Thus, the results of researches related to the improving of the corrosion resistance of copper showed that the formation of the phase composition, including intermetallic compounds CuAl2, Cu0,6Al0,4, and the oxide Cu2O, in the surface layer of copper gave a significant increase in the corrosion resistance of copper in marine and industrial environments. Electro-spark alloying of chromium, chrome-nickel steels, high-chromium iron, titanium, by electrodes from palladium and some of its alloys, contributed to the shift of corrosion potential in a positive way, by this transforming them into a passive state, and providing a substantial increase in the corrosion resistance of these metals, even in the absence of coating solidity. The results of researches on the formation of sparingly soluble surface layers on titanium and steel (with nickel galvanic coatings) by ESA to obtain corrosionproof anodes for cathodic corrosion protection of underground utilities are presented. It is shown that the passivated metals formation in the surface layer, such as Ti, Ni, intermetallic compounds, having conductivity of electronic type, favours the anodic process due to the discharge of oxygen and (or) chlorine, and not due to dissolution of the anodes themselves. Industrial tests of such anodes in the enterprises of JSC "Moldova-Gaz" showed good results, which gave reason to recommend them to use for effective protection of pipes against corrosion.