Three 2'-hydroxy chalcone derivatives were electrochemically reduced to the radical anion by a reversible oneelectron transfer followed by a chemical dimerization reaction. Under suitable conditions of the medium, the oneelectron reduction produces very well resolved cyclic voltammograms due to the formation of the radical anion. By using appropriately the wide versatility of the cyclic voltammetric technique, was possible to study the generation of the radical anion and its stability. We have found a direct relation between the A-ring substitution and the radical anion formation; consequently, it is possible to modulate the anion radical formation with different substituents on the A-ring.