For the stoichiometric compounds FeX and NiX (X = Si, Al, P) the x-ray photoelectron spectra of valence bands are obtained and calculations of their electronic structure are carried out by the tight-binding linear muffin-tin orbital atomic sphere approximation method (TB-LMTO-ASA). A satisfactory agreement between the x-ray photoelectron spectra and the calculated density-of-states curves is obtained. It is shown that with an increase of the second-component p-electrons, hybridization of d(metal) and p(X) electrons decreases, the probability of d-p resonance increases and the contribution of p(X) states near E f increases.