Direct nitridation of B4C powder has been performed at temperatures ranging from 1600 to 2250 degrees C in a stream of nitrogen gas at ambient pressure. h-BN-like layered B4CN4 powders have been prepared by nitridation of B4C at 1800 C. Carbon atoms were found to be not isolated in BN layers in B4CN4. structural model with stacked h-BN and graphite layers in a ratio 8/1 for B4CN4 is excluded. The band gap of B4CN4 was estimated to be 4 eV from the low-temperature PLE spectrum, which is much different from that of BC2N (2 eV) and that of h-BN (6 eV). The low-temperature PL spectrum of B4CN4 revealed a dominant emission band at 3.55 eV. (C) 2008 Elsevier B.V. All rights reserved.