The participation of anionic aluminum hydroxo complexes in the binding of phosphate anions on the surface of gibbsite has been shown. The succession of changes in the anionic aluminum phosphate complexes under increasing concentration of phosphate solution has been studied. It has been found that aluminum polyphosphate complexes responsible for the intensive dissolution of gibbsite are formed, along with aluminum orthophosphate complexes, at phosphate solution concentrations of 1 and 2 mol P/L. The decisive role of polyphosphate (P–O–P) groups in the ligand structure of anionic complexes in the transformation of gibbsite to a phosphate mineral (ammonium taranakite) has been revealed. The role of hydrogen bonds with the participation of ligand P(O)OH groups in the formation of ammonium taranakite crystals has been discussed.