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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 1s core to σ* and π* 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 characterize h‐BN with core absorption spectroscopy. © 1996 American Institute of Physics.