B-C-N hybrid thin films were grown from ion beam plasma of borazine (B3N3H6) on graphite substrate at room temperature, 600 ° C, and 850 ° C. The films were characterized in situ by x-ray photoelectron spectroscopy (XPS). XPS study suggested that B and N atoms in the deposited films are in a wide variety of chemical bonds, e.g., B-C, B-N, N-C, and B-C-N. The substrate temperature and ion fluence were shown to have a significant effect on the coordination and elemental binding states on the B-C-N hybrids. It was found, that B-C-N hybrid formation is enhanced at high temperature, and this component is dominantly synthesized at low fluence. The results imply that it is possible to control the composition of B-C-N hybrid by changing the ion fluence and the temperature during ion implantation. © 2005 American Vacuum Society.