We have studied the self-assembly of amphiphilic dendrons extended with linear polyethylene oxide (PEO) chains and their ion complexes. Keeping the dendron core and linear PEO chain compatible allows for the combination of dendritic core-shell and conventional blockcopolymer characteristics for complex mesophase behavior. An unexpected sequence of crystalline lamellar, cubic micellar (Pm3n), hexagonal columnar, continuous cubic (Ia3d), and lamellar mesophases is observed. Multiple phase behavior within single compounds allows for the study of charge transport and mechanical property correlations as a function of structure. The results suggest an advanced molecular design concept for the next generation of nanostructured materials in applications involving charge transport.