A simple and convenient three-step protocol for the synthesis of pentasubstituted tribromophenols based on the acid-catalyzed Grob-type fragmentation of the bicyclic ketone precursors 8a-e in high overall yield is described. The bicyclic ketones 8a-e were obtained in two steps starting from the Diels-Alder cycloadducts 5a-e of β-substituted vinyl acetates and tetrabromo-5,5-dimethoxycyclopentadiene. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.