A novel initiator, 2-benzothiazol-2-yl-5-bromomethyl-phenol (BYBP) containing excited state intramolecular proton transfer (ESIPT) fluorophore was synthesized. Atom transfer radical polymerization (ATRP) of styrene was conducted successfully using BYBP as initiator, cuprous bromide (CuBr)/N,N,N′,N″,N′-pentamethyldiethylenetriamine (PMDETA) as catalyst, and cyclohexanone/DMF (mcyclohexanone: mDMF = 1: 1) as solvent. Factors such as the reaction temperature and molar ratio of catalyst to initiator, which could affect the ATRP system, were discussed in the paper. Chain extension was conducted using polymer as the macro-initiator which was characterized via ¹H NMR. The optical property of initiator was well preserved in the obtained polystyrene, and the end-functionalized polystyrene exhibited obvious fluorescent emission at about 530 nm. [ABSTRACT FROM AUTHOR]