B as well as N core excitation spectra of hexagonal boron nitride (h‐BN) have been studied by means of x‐ray Raman scattering (XRS) spectroscopy. Transitions from 1score to &sgr;* and &pgr;* states are completely distinguished by anisotropy measurements of XRS, thus making an unambiguous assignment to the symmetries of excited states and offering a sound basis to characterizeh‐BN with core absorption spectroscopy. ©1996 American Institute of Physics.