Chemical interaction and changes in local electronic structure of Cr, Fe, Co, Ni and Cu transition metals (TMs) upon formation of an Al ₈Co ₁₇Cr ₁₇Cu ₈Fe ₁₇Ni ₃₃ compositionally complex alloy (CCA) have been studied by X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. It was found that upon CCA formation, occupancy of the Cr, Co and Ni 3d states changes and the maximum of the occupied and empty Ni 3d states density shifts away from Fermi level (E _f) by 0.5 and 0.6 eV, respectively, whereas the Cr 3d empty states maximum shifts towards E _f by 0.3 eV, compared to the corresponding pure metals. The absence of significant charge transfer between the elements was established, pointing to the balancing of the 3d states occupancy change by involvement of delocalized 4s and 4p states into the charge redistribution. Despite the expected formation of strong Al–TMs covalent bonds, the Al role in the transformation of the TMs 3d electronic states is negligible. The work demonstrates a decisive role of Cr in the Ni local electronic structure transformation and suggests formation of directional Ni–Cr bonds with covalent character. These findings can be helpful for tuning deformation properties and phase stability of the CCA.