Three polymer-amphiphile complexes were prepared by combining poly(allylamine hydrochloride) (PAH) with the potassium salt of mono-, di-, and trisubstituted benzoic acid dendrons (4-octyloxybenzoic acid, 3,5-dioctyloxybenzoic acid, and 3,4,5-trioctyloxybenzoic acid). The solid structure and properties were monitored with FT-IR, XRD, TG, DSC, and polarized optical microscope (POM). Difference in the tail chain number of the dendritic amphiphile induced two different mesomorphous structures: lamella for the mono-, disubstituted dendron containing complexes and hexagonal column for the trisubstituted dendron containing complexes. These corresponded to the ionic thermotropic liquid crystal SmA and φh phases, respectively. This finding is significant for design of functional nanostructures based on the ionic complexation of polymers and amphiphiles.