Polyvinylpyrrolidone (PVP) is a biocompatible, water-soluble polymer with unique physicochemical properties and attractive biological features that has found widespread use in several industries. Owing to advances in controlled polymerisation techniques, PVP can be easily synthesised with robust control over its architecture. However, the synthesis of PVP copolymers, which can allow tailoring of its properties and expand the scope of this polymeric material, is challenging and rarely reported. Here, we demonstrate the synthesis of well-defined, temperature-responsive polyvinylpyrrolidone-co-poly(triethylene glycol methacrylate) (PVP-co-pTEGMA) block copolymers via successive Reversible Addition-Fragmentation chain Transfer (RAFT) and Activators ReGenerated by Electron Transfer Atom Transfer Radical Polymerisation (ARGET-ATRP) techniques. We show that PVP-co-pTEGMA block copolymers display temperature-responsive behaviour and self-assemble above their cloud point temperature (Tcp) to form spherical nanostructures of 100-200 nm in diameter. Finally, we demonstrate stabilisation of these assemblies below their Tcp by cross-linking through the PVP block.