Here we disclose a method for the unexpected decarboxylative cyanide-assisted ring-opening reaction of a series of vinyl cyclic carbonates. At elevated temperature, the attack of a cyanide nucleophile at the methylenic carbon center of the organic carbonate is promoted which leads to the release of CO2 and MeCN and the intermediacy of a Michael acceptor that undergoes facile 1,4-addition affording a beta-cyano ketone product. This chemistry marks a rare ring-opening reaction that is not initiated at the typically more electrophilic carbonate carbonyl.