The morphology and interface chemistry occurring during the initial stages of growth of GaN and A1N layers has been obtained. Films were grown using gas source MBE equipment containing an ECR plasma source to activate molecular nitrogen. The experiments consisted of sequential depositions of about one monolayer thick films and XPS analysis. Evidence for silicon nitride formation on the SiC surface was obtained from the studies of both the Si oxidation states and the substrate peak intensity dependence on film thickness. The growth of GaN on sapphire appeared to occur via the Stranski-Krastanov mode, while the growth on SiC showed characteristics of three-dimensional growth. AlN grew in a layer-by-layer mode on both substrates.