This study synthesized and characterized a novel series of polyurethanes containing nonlinear optic (NLO) chromophores, which possess different dimensional or various isolation-groups. These chromophores are based on 4-(dicyanomethylene)-2-methyl-6-(p-(dimethylamino)styryl)-4H-pyran (DCM-typed dye). The NLO polyurethane containing a one-dimensional isolation-group of chromophores efficiently enhances thermal stability, but poling efficiency is not always improved as the size of isolation-group increases. The enormous isolation group restrained the mobility of chromophore in the polymer matrix and shows a worsening SH intensity. The maximum second harmonic coefficient (d(33) = 68.7 pm/V) is displayed as benzene is attaching to chromophore moieties as isolation-group in this study. Polyurethane containing two-dimensional chromophore shows superior thermal stability due to the large volume required to rotate the chromophore in the polymer matrix. Two-dimensional system exhibits lower SH intensity due to the rigid polymer main chain and twisted conjugated plane. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4937-4949, 2009