Two sets of hyperbranched polyether epoxies were synthesized to study the effect of substituent, rigidity, and nature of photoactive unit on the thermal and photoresponsive properties. Each set was comprised of one molecule with an acyclic moiety in the repeating unit, and two molecules with a cyclic moiety of varying rigidity (cycle size) in the repeating unit. Two substituents on aromatic rings in the repeating unit were present in one set, and other set was without a substituent. The mesogenic and photoresponsive properties were studied and correlated to the varied structural parameters. The effects of varied molecular structural parameters on phase behavior and photoresponsive properties were very prominent. Out of six monomeric diols, only four have exhibited liquid crystalline phase while the polymers corresponding to all monomeric diols revealed mesophase. The findings in photoresponsive properties were further supported by molecular modeling studies. The changes in refractive index, photoviscosity, and fluorescence intensity with irradiation time substantiated the spectral pattern observed in UV-Vis spectroscopy. (c) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2774-2786, 2009