We investigated the structure–property relationships between poly(vinyl acetate)-based (co)polymers and their solubility in supercritical carbon dioxide. Building on RAFT/MADIX polymerization, key macromolecular characteristics—chain length, chain-end group and composition—of these (co)polymers were studied. Their solubility in sc-CO₂ was determined by high-pressure infrared spectroscopy, thereby providing guidelines for their design.