Ozonation combined with electrolysis (ozone-electrolysis) is a new advanced oxidation process for water treatment. The advantages of ozone-electrolysis are (1) that reagents such as hydrogen peroxide or ferrous salts are unnecessary, (2) there is less influence from chromaticity, and (3) electric power is only required for operation. However, electrolysis has a serious limitation, in that it requires electrical conductivity (EC). This research is aimed at developing an ozone-electrolysis reactor that is applicable to wastewater with low EC using a cation exchange membrane as solid electrolyte. Moreover, experimental evidence of hydroxyl radical (.OH) generation via the cathodic reduction of ozone was obtained. Competitive kinetics analysis, based on the experimental data from the ozone-electrolysis of a mixed solution of 1,4-dioxane and tert-butyl alcohol, revealed that .OH contributed to 1,4-dioxane degradation. The ozone-electrolysis reactor was successfully applicable to degradation of 1,4-dioxane in both 1,4-dioxane solution (EC: less than 0.30 microS/cm) and a landfill leachate treated by a low-pressure reverse osmosis membrane (EC: 0.06 mS/cm). The use of a solid electrolyte was also very effective in reducing the electric power required for electrolysis.