A series of linear and hyperbranched polyester epoxies, with varied structural parameters such as kinked structure and different dendritic architectures, were synthesized by A(2) + B-2, A(2) + B-3, A(3) + B-2, and A(3) + B-3 approaches. The structures of synthesized monomers and polymers were confirmed by Fourier transform infrared, H-1 NMR, and C-13 NMR spectroscopic techniques. The effect of varied structural parameters on phase behavior and photoresponsive properties was investigated by using differential scanning calorimeter, thermal optical polarized microscope, UV-visible spectroscopy, photo-viscosity, and refractive index studies. The transition temperatures of hyperbranched polymers were higher than that of the corresponding linear analogues. All the polymers showed nematic phase (nematic droplets) over a broad temperature range. The effect of kinked structural unit on photoresponsive property is less in both linear and hyperbranched architectures. Although the effect of architectural nature is highly considerable within the hyperbranched architectures, the polymer (HPE-33) synthesized by A(3) + B-3 approach showed highest rate of photocrosslinking, followed by HPE-I 32; HPE-T 32, and HPE-23, which were synthesized by A(3) + B-2 and A(2) + B-3 approaches, respectively. The findings in photoresponsive properties were further supported by molecular modeling studies. Substantial variation of refractive index (0.015-0.024) indicates that these polymers could be used for optical recording. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1319-1330, 2011