Regiocontrolled halogenative cleavage of 2-methyltetrahydrofuran with various B-bromoboranes, by a predominantly SN2-type mechanism favouring the formation of primary bromide, is described. A comparative study of the relative reactivities of BH2Br·SMe2, BHBr2·SMe2, BBr3, (MeO)2BBr, and MeOBBr2 revealed that the newly synthesized (MeO)2BBr is a highly promising regioselective reagent, especially at lower temperatures.