The electrochemical behavior of dihydroxybenzenes was investigated with stationary and rotating electrodes modified by a new material, carbon atom wires (CAWs), using cyclic and differential pulse voltammetry and a hydrodynamic technique. The CAW-modified electrode showed high electrocatalytic activity to the redox of dihydroxybenzenes and capability of determining three dihydroxybenzene isomers simultaneously. The anodic peak potential on the cyclic voltammogram shifted by -0.062, -0.072, and -0.075 V in an individual hydroquinone, catechol, and resorcinol solution, respectively, at the CAW-modified glassy carbon electrode compared to a bare electrode. In a solution containing coexistent dihydroxybenzenes, 1 mmol/L for each, the anodic peak potentials of hydroquinone and catechol were apart as far as 0.151 V on the differential pulse voltammogram, and the oxidative limiting currents of both hydroquinone and catechol were linear with respect to their concentrations in the range of 1x10(-5)-10(-2) mol/L in a pH 5.0 phosphate buffer solution at the CAW-modified electrode. (c) 2007 The Electrochemical Society.