The reduction of 1,4-benzoquinone (BQ) in acetonitrile was blocked in steady-state microelectrode voltammetry although it has been believed to be a sluggish electron transfer reaction. Ferrocene was added to the BQ solution with equi-concentration in order to confirm the diffusion-control step and to evaluate accurately the kinetic effect from potential differences. Fast scan voltammograms showed the negative potential shifts both of the cathodic and the anodic peaks with an increase in the scan rate. In contrast, microelectrode voltammetry showed that the ratio of the steady-state limiting current for BQ to that for ferrocene decreased with a decrease in the electrode radii. The halfwave potential of the reduction of BQ did not vary with the radii within error. These features are largely deviated from the Butler-Volmer kinetic behavior. The electrode surface after the long term electro-reduction was coated with a precipitate. The proposed reaction mechanism is formation of films by follow-up chemical reactions of BQ associated with slight potential shift. The film blocks diffusion of BQ. This model was theoretically formulated and elucidated the experimental results. (c) 2007 Elsevier B.V. All rights reserved.