For improving glycerol decomposition, the catalysts having a unique structure were created by plasma spray technology at atmospheric pressure. The spraying system consists of direct current (DC) plasma generator (PG), plasmachemical reactor, systems of power supply and regulation, PG cooling, powder feeding and dosing. Mean temperature range of exhaust plasma jet 2800-3500 K has been established as optimal. Well-adhered Cu, CuO, Cr2O3, Ni, NiO, ZrO2, Al2O3 supported catalytic coatings with well adhered porous surface, excellent thermal and mechanical stability were deposited on stainless steel sheets. The regularities of coating deposition processes and main factors influencing them were determined. The practical application of prepared catalytic coatings for efficient glycerol conversion process has been realized. Obtained results showed, the catalytic coatings, deposited by plasma spray technology from active metal and metal oxide components, improve the output of synthetic hydrogen-rich gas production. (C) 2012 Elsevier B. V. All rights reserved.