The ordered mesa porous silica (MCM-41) thin film has been electrodeposited at the electrode surface by the method known as electrochemically assisted self assembly (EASA). The constructed structures with unique morphology have been functionalized with hydroquinone derivatives as an electron mediator. Three functionalization routes, one co-condensation and two grafting methods, have been examined for the attachment of hydroquinone derivative to the electrode surface. For all electrodes the electroactive group immobilized successfully on deposited MCM-41 thin film and all of the constructed modified electrodes show the adequate and relatively stable currents. The electrochemical behaviors of these electroactive porous electrodes and their performances in electrocatalytic oxidation of benzyl alcohol and hydrazine have been studied by electrochemical methods. (C) 2013 Elsevier Ltd. All rights reserved.