Abstract Herein, an efficient and facile approach to valuable β‐hydroxy acid derivatives from readily available aryl epoxides and CO 2 with high chemo‐ and regioselectivity under mild and sustainable electrochemical conditions is described. This approach showed broad substrate scope and good functional‐group compatibility. In addition to aryl epoxides, four‐ to six‐membered aryl cyclic ethers could all be tolerated in the reaction to provide synthetically useful hydroxy acids with high efficiency. Further late‐stage carboxylation of complex molecules and drug derivatives demonstrated its potential application in the pharmaceutical industry. Mechanistic studies disclosed possible reaction pathways.