A concise and efficient ring-opening difluorination strategy was developed for the synthesis of highly functionalized hydroxy-containing alpha,alpha-difluoro-beta-ketoamides from the one-pot multicomponent reaction of 4-aminocoumarins, NFSI, and water in dimethyl carbonate (DMC) as a green solvent. The reactions were smoothly achieved under visible light irradiation in air at room temperature without the addition of any other external photocatalysts. With this protocol, various alpha,alpha-difluoro-beta-ketoamides were successfully synthesized under mild conditions (25 examples, 73-91% yields)...