An amorphous boron–carbon–nitrogen (a-BCN) phase was synthesized by ball milling of a mixture of hexagonal BN (h-BN) and graphite with a nominal composition of (BN)0.5C0.5 in atomic ratio. Electron energy-loss spectroscopy studies indicated that the bonding of the a-BCN is in an sp2 configuration and the mixing between the BN and the C species was achieved at a nanometer scale, but the a-BCN phase was more likely a mechanical mixture rather than a chemical mixture. High-pressure and high-temperature (HPHT) treatment at 7.7 GPa and 2300 °C of the a-BCN phase resulted in complete segregation of the carbon and BN species, forming a nanocrystalline composite material comprising cubic BN (c-BN), amorphous carbon, and turbostratic graphite. The grain size of the c-BN phase was about 70 nm. No mutual solubilities between c-BN and carbon were found, and the two different species (C and BN) were well separated. An epitaxial relationship, i.e., the (0002) planes of graphite being parallel to the (111) planes of c-BN, was also found. The formation of ternary BCN phases was never found in the present experiment. Our experimental results also suggest the possibility of synthesizing c-BN grains encapsulated with graphite under controlled HPHT conditions.