In this paper we demonstrate new poly vinyl alkylate homopolymers and copolymers with excellent solubility in scCO(2) that can be used as stabilisers for dispersion polymerisation in scCO(2). Poly (vinyl acetate) (PVAc) was combined in various ratios with poly (vinyl butyrate) (PVBu) and poly (vinyl octanoate) (PVOc) to both tune the scCO(2)-solubility and provide adequate steric stabilisation. The polymer cloud points observed were found to be dependent on the ratio of the different blocks and the molecular weights and polydispersities (PDI) of the polymers. The effectiveness of these new polymeric stabilisers for dispersion polymerisation of N-vinyl pyrrolidone (N-VP) in scCO(2) is presented. Crown Copyright (C) Published by Elsevier Ltd. All rights reserved.