Metal-free oxidative bromination reactions in aqueous media were performed using tetrabutylammonium bromide, trifluoroacetic acid, and hydrogen peroxide under mild conditions. Oxidative bromination reaction of alkenes was found to afford the corresponding vic-bromides. Furthermore, this oxidative bromination system is applicable to the oxidative bromination of alkynes, arenes, and 3,4-dihydronaphthalen-1(2H)-one. A gram-scale bromination reaction was also performed successfully.