We demonstrate a valuable method to generate reactive groups on inert polymer surfaces and bond antibacterial agents for biocidal ability. Polystyrene (PS) surfaces were functionalized by spin coating of sub-monolayer and monolayer films of poly(styrene-b-tert-butyl acrylate) (PS-PtBA) block copolymer from solutions in toluene. PS-PtBA self-assembled to a bilayer structure on PS that contains a surface layer of the PtBA blocks ordering at the air-polymer interface and a bottom layer of the PS blocks entangling with the PS substrate. The thickness of PtBA layer could be linearly controlled by the concentration of the spin coating solution and a 2.5nm saturated monolayer coverage of PtBA was achieved at 0.35% (w/w). Carboxyl groups were generated by exposing the tert-butyl ester groups of PtBA on saturated surface to trifluoroacetic acid (TFA) to bond tert-butylamine via amide bonds that were further chlorinated to N-halamine with NaOCl solution. The density of N-halamine on the chlorinated surface was calculated to be 1.05x10(-5) mol/m(2) by iodimetric/thiosulfate titration. Presented data showed the N-halamine surface provided powerful antibacterial activities against Staphylococcus aureus and Escherichia coli. Over 50% of the chlorine lost after UVA irradiation could be regained upon rechlorination. This design concept can be virtually applied to any inert polymer by choosing appropriate block copolymers and antibacterial agents to attain desirable biocidal activity. (C) 2011 Elsevier B. V. All rights reserved.