The group of 1,4-dialkoxy-2,5-bis[2-(thien-2-yl)ethenyl]benzene stereoisomers was synthesized in which methoxy- and ethoxy-groups were used as alkoxy-substituents. These isomers were characterized as solution species both electrochemically and spectroscopically. As expected, these compounds, having a stilben like structure, are the subject of photoisomerization, which is described and discussed. It is demonstrated how electrochemical process may cause isomerization of the double C=C bonds in that group of compounds. An attempt of using electrochemical methods to monitor the process of photo isomerization of these compounds is presented. Mechanism of the oxidatively induced electrochemical isomerization has been proposed and discussed. The electrochemical isomerization mechanism is verified by digital simulation, which allowed estimating basic kinetic parameters of the processes. (c) 2008 Elsevier B.V. All rights reserved.