Zirconium dioxide nanomaterials, including nanoparticles and their derived films, were synthesized using a new surfactant self-assembling sol-gel route, which involves complexation of zirconium alkoxide precursor with acetylacetone as a chelating agent and Tween 20 as a structural directing agent. The properties of the synthesized material were studied using XRD, SEM, SAXS, HRTEM and N-2 adsorption and desorption analysis. It was found that Tween 20 can greatly increase the BET surface area and pore volume, inhibit crack formation in the derived film and retard particle growth at some extent. There exists tetragonal crystalline network with narrow pore size distribution in the ZrO2 nano-materials prepared with Tween 20 in the sol. Furthermore, a mechanism on the formation of mesopore ZrO2 structure via the Tween 20 self-assembling sol-gel process is presented. With the selection of the sono-gel carbon electrode modified by the mesoporous ZrO2 film (M-ZrO2 film) prepared with 1.10 g Tween 20/ml zirconia sol, enhanced electrochemical responses (i.e., enhanced peak currents) to catechol and ascorbic acid were confirmed using cyclic voltammetry (CV). Moreover, the modified electrode demonstrated additional improved electrochemical properties, such as good reversibility (i(pc)/i(pa) approximate to 1) and high selectivity (exceptionally resolved oxidation peaks between catechol and ascorbic acid), good stability and repeatability. (C) 2010 Elsevier B.V. All rights reserved.