Abstract Formation of a reversed micelle by dodecybenzenesulfonic acid (DBSH) in a dioxane–water mixed solvent was discussed in terms of the behavior of critical micelle concentration and NMR study. Hydrolysis of sucrose in the presence of the reversed micelle was then investigated. The pseudo-first-order rate constant of the reaction showed a tendency to increase with decreasing substrate concentration and increasing dioxane composition, and the maximum rate acceleration obtained in the present experiment was 21-fold on the basis of the reaction in aqueous solution. The rate acceleration may result from the solvent effect of dioxane relating to the structuredness of water and the substrate binding effect due to the formation of the reversed micelle.