A transition-metal-free and environmentally friendly synthesis method for bromobenzothiazines through tandem C–H amination/bromination was reported. This reaction contains both intramolecular C–H amination and site-selective electrophilic bromination of arenes with NaBr as the bromo source, PhI(OAc) 2 or K 2 S 2 O 8 as the oxidant, and H 2 O as the only solvent.