Poly(acrylamide)-b-complex salts made from a symmetric poly(acrylate-b-acrylamide) block copolymer, where the acrylate charges are neutralized by cationic surfactant counterions, form kinetically stable aqueous dispersions of hierarchical aggregates with a liquid-crystalline complex salt core and a diffuse hydrated shell. By the addition of suitable amounts of long-chain alcohols, such as octanol or decanol, the structure of the internal phase can be varied, producing micellar cubic, hexagonal, lamellar, or reverse hexagonal liquid-crystalline phases. In addition, a disordered reverse micellar phase forms at the highest content of octanol. These core structures are the same as those previously obtained for macroscopic homopolymer poly(acrylate) complex salt/water/n-alcohol systems at the corresponding compositions. The poly(acrylamide)-b-complex salt dispersions are kinetically stable for several weeks, with their colloidal properties and internal structures remaining unchanged. The methodology described here establishes an easy and robust protocol for the preparation of colloidal nanoparticles with variable but controlled internal structures.