A p-distyrylbenzene bearing electron-withdrawing groups on one terminal ring and electron-supplying groups on the other was synthesized and one ring was found to be significantly more electron rich than the other. Electrochemical oxidative cleavage was shown to take place predominantly at the electron-rich double bond. Selective protection of that double bond followed by anodic oxidation and deprotection afforded the product of overall anodic cleavage of the electron-deficient double bond, thus expanding the range of possible transformations of the distyrylbenzene. (C) 2013 The Electrochemical Society. All rights reserved.