The synthesis, structural, and retrostructural analysis of a library of self-assembling dendrons containing triethyl and tripropyl ammonium, pyridinium and 3-methylimidazolium chloride, tetrafluoroborate, and hexafluorophosphate at their apex are reported. These dendritic ionic liquids self-assemble into supramolecular columns or spheres which self-organize into 21) hexagonal or rectangular and 31) cubic or tetragonal liquid crystalline and crystalline lattices. Structural analysis by X-ray diffraction experiments demonstrated the self-assembly of supramolecular dendrimers containing columnar and spherical nanoscale ionic liquid reactors segregated in their core. Both in the supramolecular columns and spheres the noncovalent interactions mediated by the ionic liquid provide a supramolecular polymer and therefore, these assemblies represent a new class of dendronized supramolecular polymers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4165-4193, 2009