The possibility of using an aqueous non-toxic electrolyte of ammonium nitrate and glycerin for the cathodic plasma electrolytic nitrocarburizing of low-carbon steel is considered in this paper. Surface morphology and roughness, element and phase compositions, and microhardness of the modified layer were investigated. Kinetic calculations of the processes of nitrogen and carbon diffusion into the steel surface are proposed, taking into account their mutual influence. Wear resistance was studied under dry friction conditions with tool alloy steel as a counter-body. Corrosion studies are performed using potentiodynamic polarization curves in 3.5% sodium chloride solution. The plasma electrolytic nitrocarburizing in an aqueous electrolyte with ammonium nitrate and glycerin is established to increase surface hardness up to 980 HV due to the formation of a nitrocarburized layer with 1.35 ± 0.12% carbon and 0.32 ± 0.08% nitrogen concentration. The influence of erosion in electrolyte plasma and high-temperature oxidation on the morphology and surface roughness is shown. The presence of a dense oxide layer, low surface roughness, and high hardness of the diffusion layer favor a decrease in the friction coefficient by 1.3 times, weight wear by 1.8 times and corrosion current density by 1.4 times.