A one-pot synthetic route based on copper-catalyzed Huisgen reaction has been developed to functionalize a methacrylate propargylic polymer with azido-substituted moieties. This procedure was used for the preparation of electro-optic materials containing well-known Disperse Red One (DR1) chromophores along with bulky adamantyl moieties (Adam). The postfunctionalization of the propargylic polymer was successfully achieved using different molar ratios of DR1/Adam. These novel polymers exhibit high glass transition temperature owing to the rigid structure of adamantyl units. Moreover, the second harmonic generation measurements demonstrated the effectiveness of adamantyl groups to act as insulating shield limiting thus the electrostatic interactions between chromophores. Indeed, higher optimal chromophore concentration (50 mol %) than in conventional DR1-containing polymers (30 mol %) allowed us to increase the d(33) coefficient up to 92 pm/V. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5652-5660, 2009