Novel AB(2)-type azide monomers such as 3,5-bis(4-methylolphenoxy)carbonyl azide (monomer 1), 3,5-bis(methylol)phenyl carbonyl azide (monomer 2), 4(methylol phenoxy) isopthaloyl azide (monomer 3), and 5-(methylol) isopthaloyl azide (monomer 4) were synthesized. Melt and solution polymerization of these monomers yielded hydroxyl- and amine-terminated hyperbranched polyurethanes with and without flexible ether groups. The structures of theses polymers were established using FT-IR and NMR spectroscopy. The molecular weights (M,) of the polymers were found to vary from 3.2 x 10(3) to 5.5 x 10(4) g/mol depending on the experimental conditions used. The thermal properties of the polymers were evaluated using TGA and DSC: the polymer obtained from monomer (1) exhibited lowest T, and highest thermal stability and the polymer obtained from monomer (2) registered the highest T-g and lowest thermal stability. All the polymers displayed fluorescence maxima in the 425-525 nm range with relatively narrow peak widths indicating that they had pure and intense fluorescence. Also, the polymers formed charge transfer (CT) complexes with electron acceptor molecules such as 7,7,8,8-tetracyano-quinodimethane (TCNQ) and 1,1,2,2-tetracyanoethane (TCNE) as evidenced by UV-visible spectra. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3337-3351, 2009