Block copolymers of N-vinyl pyrrolidone (NVP) and benzyl methacrylate (BzMA), PNVP-b-PBzMA, were prepared by RAFT polymerization techniques and sequential addition of monomers. The copolymers were characterized by Size Exclusion Chromatography (SEC) and NMR spectroscopy. Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA) and Differential Thermogravimetry (DTG) were employed to study the thermal properties of these copolymers. The micellization behavior in THF, which is a selective solvent for the PBzMA blocks, was examined. For comparison the self-assembly properties of the corresponding statistical copolymers, PNVP-stat-PBzMA, were studied. In addition, the association behavior in aqueous solutions was analyzed for the block copolymers, PNVP-b-PBzMA. In this case, the solvent is selective for the PNVP blocks. Dilute solution viscometry, static (SLS) and dynamic light scattering (DLS) were employed as the tools to investigate the micellar assemblies. The efficient encapsulation of the hydrophobic curcumin within the micellar core of the supramolecular structures in aqueous solutions was demonstrated by UV-Vis spectroscopy and DLS measurements.