<p>Star-shaped six-arm polymers with hexaaza[2₆]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization. The ratio of blocks, the order of their attachment to the core, and arm length were varied. Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics. It has been shown that star-shaped molecules were characterized by high intramolecular density, and the arm folding increased with their lengthening. The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established. Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated. The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods. The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed. A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.</p>