The reduction of dimethoxycalix[4]arenediquinone in acetonitrile solution and the subsequent electrodeposition of calix[4]arenequinhydrone association on platinum electrode has been investigated. The formation of calix[4]arenedihydroquinone has been detected during the electrochemical generation calix[4]arenediquinone by the anodic oxidation of 5,11,17,23-tetra-tert-butyl-26,28-dimethoxycalix[4]arene-25,27-diol. By using cyclic voltammetry study, it is shown that in potentiodynamic and potentiostatic experiments, the electrochemical reduction of calix[4]arenediquinone leads to the formation of its corresponding calix[4]arenedihydroquinone and the subsequent organization of quinhydrone, which electrodeposits on the surface of disk electrode. In both solutions, the generation of protonated form of the reduced product has been detected by the appearance of two successive oxidation/reduction systems at about 0.7 and 1.2 vs SCE/V, respectively. Besides, the electroactive films showed during the anodic scanning one oxidation/reduction system at 1.0 vs SCE/V and two overlapped waves between 1.7 and 2.2 vs SCE/V. Two reduction/oxidation systems are also noted in the cathodic direction between 0.7 and 1.6 vs SCE/V. (C) 2011 Elsevier Ltd. All rights reserved.