The synthesis and characterization of two families of ionic liquid crystal dendrimers consisting of the ammonium salts of the commercially available poly(amidoamine) (G = 0−5) and poly(propylene imine) (G = 1−5) dendrimers and three long-chain carboxylic acids are reported. The liquid crystalline behavior was investigated by means of differential scanning calorimetry, polarizing light optical microscopy, and X-ray diffractometry. The thermal stability of the ionic materials was further studied by NMR. Most of the dendrimers show lamellar mesomorphism, and two of them exhibit columnar mesomorphism. On the basis of the experimental results, we propose models both at the molecular level and in the mesophase for all the materials.