Successful crystallization and X-ray crystallographic analyses of the highly metastable (1 : 1) complexes of bromine with benzene and toluene establish the unique ( localized) structure B that differs in notable ways from the long-accepted (delocalized) structure A. Furthermore, we demonstrate the ( highly structured) charge-transfer complexes [C6H6,Br-2] and [CH3C6H5,Br-2] to be the pre-reactive intermediates that are converted ( via an overall Br+ transfer) to the Wheland intermediates in electrophilic aromatic bromination. The role of the dative ion pairs [C6H6.+Br2.+] and [CH3C6H5.+Br2.+] in the rate-limiting activation processes is underscored.