Norbornene-dicarboximide derived polymer brushes containing Disperse Red 1 appended chromophores have been prepared by sequencial ring opening metathesis polymerization and atom transfer radical polymerization. This brush was then employed as an electro-optic polymer host for high molecular hyperpolarizability phenyl vinylene thiophene vinylene (FTC) bridge chromophores in a binary chromophore system. The r33 of the polymer brush/bi-chromophore network was evaluated via in situ poling and was measured as 94 pm/V compared to the benchmark polymethylmethacrylate (PMMA) system of 76 pm/V with an identical chromophore. Furthermore, our polymer brush/bi-chromophore network exhibited an enhanced poling efficiency of 1.37 (nm/V)(2) as compared to a simple PMMA - FTC host - guest 0.70 (nm/V)(2). (C) 2013 Elsevier B.V. All rights reserved.