Novel alpha-bromo-beta-phosphoalkoxylated carbonyl compounds were produced in moderate to excellent yields via highly selective four-component reaction involving NBS, a cyclic ether, an organic phosphate and an aromatic alpha,beta-unsaturated carbonyl compound. A number of experimental observations suggested that the reaction is likely initiated by an acid mediated nucleophilic conjugate addition followed by electrophilic trapping the enol intermediate and subsequent ring-opening of the cyclic ether.