Polyelectrolyte-based complexes have attracted attention, as the interaction of the oppositely charged components results in nanoparticle formation through an easy but highly efficient method, avoiding the use of strong solvents, extreme temperatures, and toxic chemicals. Sodium oleate (NaOL) is a widely used surfactant in the pharmaceutical industry due to its availability, eco-friendliness, and low cost. In the present study, the neutral-cationic block copolymer poly(oligo(ethylene glycol) methyl ether methacrylate)–b–quaternized poly(2-(dimethylamino) ethyl methacrylate) (POEGMA-b-Q(PDMAEMA)) is mixed with the anionic surfactant sodium oleate for the formation of nanoscale polyelectrolyte complexes through electrostatic interactions. Different weight ratios of copolymer to surfactant are studied. Then, the co-solvent protocol was implemented, and curcumin is successfully loaded in the formed particles for drug delivery applications. The size and morphology of the macromolecular complexes are examined via Dynamic Light Scattering (DLS) and Cryogenic Transmission Electron Microscopy (cryo-TEM). The methods that we have used have indicated that the polymer–surfactant complexes form spherical complexes, worm-like and vesicle-like structures. When curcumin was introduced, encapsulation was effectively achieved into micelles, giving rise to vesicle-like shapes. The success of curcumin encapsulation is confirmed by Ultraviolet–Visible absorption (UV–Vis) and fluorescence (FS) spectroscopy. POEGMA-b-Q(PDMAEMA)–sodium oleate polyelectrolyte complexes revealed promising attributes as efficient drug carrier systems for pharmaceutical formulations.