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.