The results of systematic studies of the electrospark alloying process with the introduction of dispersed materials into plasma of low-voltage pulsed discharges are presented. Technological methods have been developed for supplying the powder material straight into the treatment zone through a hollow electrode of an anode or from the side, with the electrode-anode periodically contacting the substrate of cathode. It has been established that under the same energy regimes, when powder materials were introduced into the discharge zone, the increase in the mass of the cathode per time unit increases from 10 to 15 times or more. This study presents the process of synthesis of carbide phases (TiC and WC) during electrospark alloying of steel substrates with electrodes made of Ti, W, and graphite, with additional supply powders of these materials into the processing zone. A process has been developed for the synthesis of ternary compounds, so-called MAX-phases: Ti₂AlC, Ti₂AlN and Ti₃SiC₂ by electrospark alloying with powder compositions TiAlC, TiAlN and TiSiC. These MAX phases exhibit a unique combination of properties that are characteristic of both metals and ceramics. Energy modes of the processing were optimized, which resulted in high-quality coatings with the maximum content of carbide phases and ternary compounds. It has been established that the energy of electrical pulses during electrospark alloying, when powders of materials are fed into the interelectrode gap, ranges from 0.8 to 3.0 J, depending on their thermal physical properties. High wear and corrosion resistant characteristics of C45 structural steel with such electrospark coatings are obtained. The wear of steel with coatings in comparison with uncoated steel decreased by an average of 5.5–6.0 times. It was estimated the high corrosion resistance of 40X13 steel coated with TiC and WC in 3% NaCl solution. The corrosion current for these coatings is 0.044 and 0.075 A/cm², respectively, and is significantly less than for coatings made of TiAlC, TiAlN, and TiSiC compositions. X-ray phase and optical metallographic microscopy analyses enabled the display of the amorphous-crystalline nature of the coatings.