Treatment of N-bromosuccinimide (NBS) with (carboethoxymethylene) triphenylphosphorane (1) in CH(2)Cl(2) followed by the addition of an alcohol in the presence of manganese dioxide under ultrasonic irradiation constitutes a stereoselective one-pot procedure for the preparation of Z-configured alpha-bromo-alpha,beta-unsaturated esters in good to excellent yield.