New hydroxyl substituted 3-arylbenzo[f]coumarins (compounds 6-10) have been designed and synthesized. Their electrochemical redox mechanisms, and the influence of one or two hydroxyl groups, in different positions on the coumarin scaffold, was investigated by cyclic, differential pulse and square wave voltammetry, at a glassy carbon electrode, at different pHs, and a comparative study was performed. The structural information obtained enabled a better understanding of the structure/electrochemical relationship of hydroxyl substituted 3-arylbenzo[f]coumarins, compounds with important antioxidant properties. (C) 2014 Elsevier B.V. All rights reserved.