BN 2-vinylnaphthalene (BN2VN) is a novel precursor to vinyl alcohol copolymers via sodium hydroperoxide oxidation. We show that the unusual aromaticity of the BN heterocycle leads to styrene-like reactivity. Computational data including structural parameters and nucleus independent chemical shift (NICS) values support the aromaticity of the BN naphthalene side chain of BN2VN. Styrene (St) and BN2VN reactivity ratios (r(1)(BN2VN) = 0.423; r(2)(St) = 2.30; r(1)r(2) = 0.97) were determined by nonlinear least-squares (NLLS) statistical methods. We demonstrate control of copolymer physical properties, including glass transition temperature. This work outlines design principles for the synthesis of tailored polymeric styrene-vinyl alcohol architectures.