Complexation of dendronized block copolymers with sulfate alkyl tails forms unprecedented hierarchically ordered bulk structures, including rectangular-in-lamellar, tetragonal-in-lamellar, hexagonal-in-lamellar and lamellar-in-lamellar. These novel liquid-crystalline morphologies, which can be designed at low length scales in these systems, are expected to provide final materials with not only unprecedented structural complexity, but also tunable physical properties.