Hexagonal boron carbonitride (h-BCN) films have been synthesized on silicon (100) substrate by radio frequency plasma enhance chemical vapor deposition from tris(dimethylamino)borane (TDMAB) as a precursor. XPS and FT-IR revealed that the film with a composition of B46C18N36 had sp(2) B-C-N atomic hybridization. NEXAFS suggested that the local structure of BCN showed different atomic orientations to the substrate.