Hydrodynamic and optical methods were applied to study conformational and physical properties of hyperbranched pyridylphenylene polymers in dilute solutions. The samples were synthesized using Diels–Alder polycyclocondensation. It was demonstrated that hydrodynamic properties of the studied macromolecules were typical for compact non-percolated spheres. Optical and electro-optical methods revealed information regarding the shape and asymmetry of the macromolecules (p ≈ 1.4). The contributions of optical shape effect to the observed flow birefringence of polypyridylphenylene solutions and intrinsic anisotropy of polarizability were evaluated and analysed. It was shown that varying the polymer composition (i.e. the degree of branching) caused considerable changes in the anisotropy of optical polarizability of the polymers. Dramatic difference of the electro-optical properties in non-polar (toluene) and polar (tetrachloroethane) solvents was found; this difference was related to the orientational correlation of