All-trans-retinoic acids (ATRA) are ionically complexed with cationic polyelectrolytes containing tertiary amines and self-assembled into nanoscale colloidal structures. Poly(2-(dimethylamino)ethyl methacrylate) grafted with polyethylene glycol, poly(DMAEMA-g-PEG), is used as a double hydrophilic, cationic polyelectrolyte. The polyion/ATRA complexes are formed by adding ATRA in dimethyl sulfoxide into aqueous solution of poly(DMAEMA-g-PEG). This complexation effectively suppresses the formation of undesirable drug crystallites and produces stable colloidal nanostructures having a hydrodynamic diameter of about 15 nm at a neutral pH. However, as the pH decreases below about 6, they undergo dramatic structural change into large aggregates of about 250 nm in diameter presumably due to the dissociation of ATRA from the polyelectrolyte. We expect that this pH-sensitive response of the polyion/ATRA complexes is useful for intracellular translocation at a neutral pH followed by the endosomal escape of ATRA in an acidic condition.