We have investigated the DBU-promoted HBr-elimination of vicinal dibromides having an adjacent O- and/or N-functional group under mild basic conditions. The elimination of 1-oxygen-functionalized 2,3-dibromopropanes was more regioselective than that of 1-nitrogen-functionalized 2,3-dibromopropanes. This observation suggests that the elimination selectivity is affected by the electronegativity of the neighboring heteroatoms themselves and not by the entire functional group.