This article presents a study of the reactive deposition of coatings by the Pulsed Magnetron Sputtering method with reversely biased electrodes, where the cathode is sputtered at ground potential and an anode, separated from the magnetron body, is positively biased. The reactive sputtering of grounded cathodes occurs by glow discharge plasma localization at the surface of the cathode enhanced by a magnetic field. Our study compares the process of coating deposition running at standard for a magnetron sputtering method with an electrode arrangement which is reversely biased. Processes of coating deposition were carried out in various mixtures of sputtering and reactive oxygen/nitrogen gases. The structure and phase composition of TiO2 and TiN coatings were examined. In the case of the magnetron system with reversed electrodes biasing we spotted the tendency of nucleation in the rutile phase in the structure of TiO2 coatings. TiN coatings deposited by this version of magnetron sputtering were characterized by better stoichiometry. We believe that a specific electric field distribution for the magnetron system with a grounded cathode strongly affects the mechanism of synthesis which enhances the reactivity, and thermodynamically stabilizes phases characterized by high barriers of nucleation. (C) 2017 Elsevier B.V. All rights reserved.