We synthesized molecules containing one or two dendritic segments and a rigid-rod-like segment with their structures in the solid state. The molecules with rod-dendron or dendron-rod-dendron architecture had biphenyl ester rigid segments and 3,4,5 tris(re-dodecyloxy)benzoate of first or second generation as their dendritic segments. The variables investigated included the rod segment length as well as dendron generation, and all materials obtained were characterized by optical microscopy, differential scanning calorimetry, and X-ray scattering. Depending on the size of the rod segment and generation number of the dendritic segment, molecules organized into smectic, columnar, or cubic phases, and the symmetries observed were dominated by the anisotropic rod-rod interactions. © 2003 Wiley Periodicals, Inc.