Binary complexes of α-hydroxy acids (L-Tartaric acid and L-Malic acid) with d-electron metal ions (copper, cobalt, nickel) were investigated. Potentiometric measurements have been performed in aqueous solution with computer analysis of the data for determination of the stability constants of complexes formed in the studied systems. The coordination mode of the complexes was defined using spectroscopic methods: electron paramagnetic resonance (EPR), ultraviolet-visible (UV-Vis), circular dichroism (CD), and infrared (IR). Results of the equilibrium studies have provided evidence for the formation of dimers with copper(II) ions and monomers with cobalt(II) and nickel(II) ions.