We have successfully developed a novel electrolytic system for non-Kolbe electrolysis based on the acid-base reaction between carboxylic acids as a substrate and solid-supported bases. It was found that the acid-base reaction between carboxylic acids and solid-supported bases preferentially takes place to reduce the cell voltage in MeOH. On the basis of the electrolytic system, non-Kolbe electrolysis of various carboxylic acids was carried out to provide the corresponding methoxylated products in excellent yields.