The features of molecular and electronic structures of complex compounds derived from azopyrazolone derivatives are reviewed. Despite the wide use of metal-containing azopyrazolone dyes for more than 1.5 centuries, little information on their molecular structure is found. Our recent researches allowed the introduction of new coordination modes of azopyrazolone derivatives at complexation with metals. Together with traditional bi- and tridentate coordination, the possibility of an N pyrazolone atom to be involved in coordination was also found. As a result, polymeric or polynuclear complexes were isolated and described by X-ray analysis, NMR, EPR, IR, and UV spectroscopy. The analysis of the interatomic distances in the organic anions indicated that azopyrazolone derivatives do not undergo significant azo-hydrazo tautomeric transformations at ionization and complexation despite strong shifts of the absorption bands in their IR and UV-VIS spectra. © 2018 Walter de Gruyter GmbH, Berlin/Boston.