The fabrication of nanoporous thin films of brominated polystyrene-block- poly(methyl methacrylate) (PBrS-b-PMMA) copolymers by using UV cross-linked PS matte for mediating preferential interfacial interactions to achieve the perpendicular orientation of the microdomains has been reported. Molecular weights and PDI were characterized by gel permeation chromatography (GPC), and the compositions of copolymers were determined by H nuclear magnetic resonance (NMR) with mass densities of two components. Combining mediation of interfacial interactions and solvent annealing produced the nanoporous PBrS-b-PMMA thin film with perpendicular orientation and a high degree of lateral ordering. A particularly attractive feature of PBrS-b-PMMA copolymers is that active Br atoms provide an easy way to functionalize PBrS-b-PMMA copolymer thin films through palladium- catalyzed coupling reactions.