CNx/TiNy multilayers were prepared by ion-beam sputtering and analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive X-ray (EDX). EDX results show that the atom ratios of [N]/([C]+[N]+[Ti]) in the multilayers vary from 20 at.% to 41 at.%. XPS analysis presents that the N content of the CNx layer in CNx/TiNy is about 32.18 at.%. The nature of chemical bonding of the CNx layer in CNx/TiNy was also analyzed. The X-ray and electron diffraction analyses suggest that three kinds of C3N4 phases, such as beta-C3N4, graphite-C3N4 and cubic-C3N4, are embodied in the multilayers. In CNx/TiNy bilayers, a hetero-epitaxial relationships, of (1 1 2) cubic-C3N4//(1 1 13) Ti2N, and [42 (3) over bar] cubic-C3N4//[1 (1) over bar 0] Ti2N, was observed between cubic-C(3)N4 and Ti2N. (C) 2003 Kluwer Academic Publishers.