The valence and conduction band states of crystalline silicon nitride &agr;‐Si3N4have been studied by using two complementary experimental methods. The total valence band distribution has been analyzed by x‐ray induced photoelectron spectroscopy. The Si 3pvalence states and the Sipconduction states have been probed selectively by x‐ray emission and absorption spectroscopies, respectively. The experimental curves have been compared in the same energy scale referred to the Fermi level. Our results show clearly that the N 2p&pgr; states of Si3N4are located at the top of the valence band while Si 3pstates, mixed to N 2pstates and, respectively, to N 2sstates are located at aboutEF−8.4 eV andEF−19.6 eV. Our experimental results are in very good agreement with theoretical simulations of the spectra made from recent density of states calculations by Robertson [Philos. Mag. B63, 47 (1991)] in a tight binding approach.