omega-Hydroxy-functionalized oligo(N-vinyl-2-pyrrolidinone) (PVPOH) was prepared by chain-transfer radical polymerization in the presence of 2-isopropoxyethanol as the chain-transfer agent, and grafter onto dextran. Two PVP-Dex graft copolymers were obtained starting from different PVPOH/dextran weight ratios in the feed, namely 2:1 and 5:1. The variation of molecular weight distributions, combined with the results of solubility tests and of selective extractions in organic solvents, irrefutably confirmed the successful grafting reactions and the efficacy of the purification procedures applied.