Atom transfer radical polymerization (ATRP) of MMA was conducted successfully at ambient temperature (25°C) using 2-bromomethyl-4,5-diphenyloxazole as initiator, CuBr/2,2′-bipyridine (BPY) as catalyst, and 1,4-Dioxane as solvent. Factors such as the reaction temperature, mole ratio of monomer and catalyst to initiator, solvent and so on, which can affect the ATRP system, were discussed in the paper. Chain extension was conducted using polymer as the macro-initiator which was characterized via 1 H NMR. The optical property of initiator was well preserved in the obtained PMMA, and the end-functionalized PMMA exhibited obvious fluorescent emission at 367nm.