Energy distributions and properties of the occupied and empty electronic states for a planar complex of nickel porphyrin NiP are studied by X-ray photoemission and absorption spectroscopy techniques. As a result of the analysis of the experimental spectra of valence photoemission, the nature and energy positions of the highest occupied electronic states were determined: the highest occupied state is formed mostly by atomic states of the porphine ligand; the following two states are associated with 3d states of the nickel atom. It was found that the lowest empty state is specific and is described by the σ-type b1g MO formed by empty $$Ni3{d_{{x^2} - {y^2}}}$$ N i 3 d x 2 − y 2 -states and occupied 2p-states of lone electron pairs of nitrogen atoms. This specific nature of the lowest empty state is a consequence of the donor–acceptor chemical bond in NiP.