Oxybromination of aromatic compounds by high-valent metal-oxo intermediates has yet to be explored despite extensive studies on the oxybromination of aliphatic C-H bonds of hydrocarbons. Herein, we report the regioselective oxybromination of methoxy-substituted benzenes by a nonheme Mn-IV-oxo complex binding scandium ions, [(Bn-TPEN)Mn-IV(O)](2+)-(SC-(OTf3)(2) (1), in the presence of tetrabutylammonium bromide. The regioselective oxybromination occurs at the carbon atom with the highest positive charge via electron transfer (ET) from the methoxy-substituted benzenes to 1. ET driving force dependence of the rate constants of ET from methoxy-substituted benzenes to 1 is well fitted in light of the Marcus theory of ET. Under photo-irradiation, the oxybromination of benzene by 1 can be achieved via ET from benzene to the photoexcited state of 1, although no reaction occurs between benzene and the ground state of 1 in the dark. To the best of our knowledge, this is the first example of reporting the stoichiometric regioselective oxybromination of the benzene ring by a synthetic high-valent Mn(IV)-oxo complex and the catalytic regioselective oxybromination reaction with a Mn(II) complex and a terminal oxidant.