This paper overviews the relatively new surface engineering discipline of plasma electrolysis, the main derivative of this being plasma electrolytic deposition (PED), which includes techniques such as plasma electrolytic oxidation (PEO) and plasma electrolytic saturation (PES) processes such as plasma electrolytic nitriding/carburizing (PEN/PEC). In PED technology, spark or arc plasma micro-discharges in an aqueous solution are utilised to ionise gaseous media from the solution such that complex compounds are synthesised on the metal surface through the plasma chemical interactions. The physical and chemical fundamentals of plasma electrolysis are discussed here. The equipment and deposition procedures for coating production are described, and the effects of electrolyte composition and temperature on ignition voltage, discharge intensity and deposited layer thickness and composition are outlined. AC-pulse PEO treatment of aluminium in a suitable passivating electrolyte allows the formation of relatively thick (up to 500 μm) and hard (up to 23 GPa) surface layers with excellent adhesion to the substrate. A 10-20 μm thick surface compound layer (1200HV) and 200-300 μm inner diffusion layer with very good mechanical and corrosion-resistant properties can also be formed on steel substrates in only 3-5 min by use of the PEN/PEC saturation techniques. Details are given of the basic operational characteristics of the various techniques, and the physical, mechanical and tribological characteristics of coatings produced by plasma electrolytic treatments are presented.