The BN and BCNO phosphors were prepared at 750°C using different methods and their structure and luminescent properties were investigated. All the prepared samples were turbostratic boron nitride structure. The SEM and high-resolution TEM images show that the BCNO phosphors are polycrystalline in nature and include some nanocrystals. The carbon and oxygen impurities have great effects on the excitation, emission, and absorption spectra of BN and BCNO phosphors. The first-principle calculations results indicate that the carbon and oxygen impurities will produce energy levels in the band gap, which can affect the spectra properties of BCNO phosphors. The spectra properties of BN and BCNO phosphors can be well explained by a simplified energy level diagram.