AbstractA rhodium(I)‐catalyzed decarboxylative hydroacylation of readily available vinylethylene carbonates with salicylaldehydes for regioselective preparation of esters was developed. Reaction optimization revealed that methacrylamide might promote the hydroacylation by bidentate chelation assistance to the cationic rhodium. Mechanistic findings suggested that this one‐pot coupling reaction proceeds via Markovnikov hydrorhodation‐initiated site‐selective β‐C−O bond cleavage with concurrent release of CO2.magnified image