The synthesis, characterization and the self-assembly process of a novel biodegradable block copolymer containing a poly(epsilon-caprolactone), PCL, central block and three poly(N-vinyl-2-pyrrolidone), PVP, arms are reported. Three samples with different amounts of PVP were investigated. The copolymers were characterized by FTIR spectroscopy, (1)H NMR and viscosity measurements. The composition and the molecular weights of the block copolymers were established using size exclusion chromatography SEC and (1)H NMR. Micelle formation by these copolymers was monitored by using the vibrational fine structure of pyrene monomer fluorescence and the critical aggregation concentrations, cac, of the copolymers in aqueous solution were determined using sigmoid Boltzmann-type fitting of the fluorescence data. Dynamic light scattering measurements showed a bimodal size distribution for the copolymers in solution, indicating that the micellization is an intermolecular process. Partitioning coefficients of pyrene between copolymer micelles and water were also determined and increase in magnitude with increasing epsilon-caprolactone content of the copolymer.