Structural-phase transformations in 0.34C–1Cr–1Ni–1Mo–Fe steel during plasma electrolytic hardening were investigated. Electrolytic-plasma hardening of steel samples was carried out by surface quenching with rapid concentrated heating of the surface by plasma action and subsequent rapid cooling by heat removal from the depth of the sample by electrolyte jet. Plasma electrolytic hardening was carried out in the cathode mode in an electrolyte made from an aqueous solution containing 20 % sodium carbonate and 10 % carbamide. To study the structural-phase states of the modified layer, we used the method of transmission diffraction electron microscopy on thin foils. The study of steel samples was carried out before and after the plasma electrolytic hardening. Initially, the steel was a mixture of pearlite and ferrite grains. Surface hardening of 0.34C–1Cr–1Ni–1Mo–Fe ferrite-pearlite steel led to a change in the structural-phase state and the formation of a packet-lamellar martensite structure. It was found that PEH leads to distortion of the crystal lattice and the formation of long-range internal stresses, as well as to the release of small particles of cementite and carbide of M23C6 type, uniformly distributed throughout the volume of the material. Surface hardening led to the increase in all quantitative parameters of the fine structure (ρ, ρ ±, χ, σL, σd).