Enantioselective radical reactions mediated by TBADT have seldom been seen due to the inherent challenges. Herein, we disclose a new chiral hydrogen atom transfer (HAT) reagent that was generated easily from 8H-BINOL, potassium carbonate, and TBADT under irradiation. The new complex 8H-BINOL/DTs could be used as a chiral H donor. A series of azaarenes could be converted into the corresponding chiral compounds via radical addition followed by enantioselective HAT.