Modification of commodity aromatic polymers is highly desirable for accessing materials with new properties. The long-standing challenge for such approaches lies in the development of catalytic methods that can functionalize the aromatic polymers with high precision while preserving the molecular weight and distribution of the starting polymers without any alteration. Herein, we report a highly efficient AuCl3-catalyzed site-selective aromatic C-H halogenation of polystyrene. The most important feature of this method is that the degree of halogenation can be precisely controlled by simply changing the loading of the halogenating agent, thus allowing the tuning of functional group density in an accurate and predictable manner. Various functional groups, including NH2 and Bpin, can be installed through effective derivatization of the resultant brominated polystyrene, thus making the method a valuable strategy for the synthesis of value-added materials with tailored properties.