Polyvinylpyrrolidone (PVP) is a commonly used polymer with many different applications in the pharmaceutical, cosmetic and food industries. However, the lack of reactive groups and the difficulty in copolymerizing the monomer, Nvinylpyrrolidin-2-one (NVP) with most other monomers, limits the possibility of modifying the physical and chemical properties of the polymer. Monomers that are derivatives of NVP itself are expected to show small differences in radical reactivity as compared to the parent monomer and provide a way of adjusting the polymer properties without extensive compositional drift during copolymerization. Here we present the synthesis of two new functionalized NVP-based monomers and their copolymerization with alkylated NVP-monomers for the preparation of two functionalized PVPs with phase-selective solubility in heptane. Both copolymers snowed 99.99% selective solubility in heptane over DMF (thermomorphic system) and 99.99% in heptane over 90% EtOH-H2O (latent biphasic system). These results suggest that the polymers could be used as soluble supports to facilitate recovery and recycling of catalysts or reagents from liquid/liquid systems after homogeneous reactions. 2006 WILEY-VCH Verlag GmbH & Co. KGaA.