Polyols based on oligo(vinylacetate) were synthesized using a convenient one-pot, two-step process. Polymerization of vinylacetate was performed in 2-propanol as a chain-transfer agent using di-tert-butylperoxide as a free-radical initiator. Saponification of the oligomers was performed in both tetrahydrofuran and 2-propanol using stoichiometric amounts of methanol in the presence of a basic catalyst. Well-defined oligo(vinylacetate-co-vinylalcohol) polyols with a degree of polymerization below 12 and a hydroxyfunctionality smaller than 4 were obtained. Oligo(vinylacetate-co-vinylalcohol) was used as a polyol component in the formation of polyurethanes.