In this paper we describe an approach for the formation of composite layers on the surface of refractory metals. We show that laser radiation on refractory metals (Ti, V, Zr, Mo, Hf, Ta, and W) immersed in liquid nitrogen can provide a chemical synthesis of nitride phases on the surface of metals. The metals were subjected to pulsed laser radiation with a wavelength of 1.06 mu m. The power density ranged from 104 to 1 09 W cm(-2). The synthesis of nitrides began with the formation of MexNy (x > y) phases with low contents of nitrogen. When the melting point was reached at the metal surface, the quantity of MeN phases increased sharply. Study of the melting zone showed that it contained a non-uniform distribution of nitride phases. The quantity of nitrides was a maximum on the surface and decreased with the increase of the depth of melting zone. Due to the 14 high-cooling rates, titanium nitride crystallized in the form of columns. Maximum microhardness in the Ti surface layer was up to 20,000 MPa. (C) 2007 Elsevier B.V. All rights reserved.