Poly(N-vinylpyrrolidone)-block-poly(vinyl acetate) (PVP-b-PVAc) block copolymers of varying molar mass and hydrophobic block lengths were synthesized by xanthate-mediated radical polymerization. In order to control the molar mass of the hydrophilic PVP block, a xanthate chain transfer agent, S-(2-cyano-2-propyl) O-ethyl xanthate, was used. The PVP-b-PVAc block copolymer is composed of a hydrophilic and hydrophobic segment, and has the ability to self-assemble in aqueous solution. The PVP-b-PVAc block copolymers were characterized by H-1 NMR spectroscopy to confirm their self-assembly in water. The critical micelle concentration was determined by fluorescence spectroscopy. A combination of dynamic light scattering, transmission electron microscopy, and static light scattering was used to further characterize the self-assembly of the block copolymers in water.