Oxyquinolyl end group functionalized PMMA was prepared by a new initiator 5-chloromethyl-8-hydroxyquinoline via atom transfer radical polymerization. Studying this polymer, we find it possesses stronger fluorescence and larger nonlinear third-order optical (NLO) coefficient than the PMMA initiated by ethyl alpha-bromoisobutyrate, and the polymer could be easily processed into film. The NLO coefficient of the polymer tested in the film is better than that in the solution.