This article is the first comprehensive review on the study and use of vinyl ester monomers in reversible addition fragmentation chain transfer (RAFT) polymerization. It covers all the synthetic aspects associated with the definition of precision polymers comprising poly(vinyl ester) building blocks, such as the choice of RAFT agent and reaction conditions in order to progress from simple to complex macromolecular architectures. Although vinyl acetate was by far the most studied monomer of the range, many vinyl esters have been considered in order to tune various polymer properties, in particular, solubility in supercritical carbon dioxide (scCO₂). A special emphasis is given to novel poly(vinyl alkylate)s with enhanced solubilities in scCO₂, with applications as reactive stabilizers for dispersion polymerization and macromolecular surfactants for CO₂ media. Other miscellaneous uses of poly(vinyl ester)s synthesized by RAFT, for instance as a means to produce poly(vinyl alcohol) with controlled characteristics for use in the biomedical area, are also covered.

RAFT/MADIX polymerisation of vinylphosphonic acid (VPA) was controlled in water with an O-ethyl xanthate transfer agent. This represents the first example of reversible deactivation radical polymerisation of a monomer bearing an unprotected phosphonic acid function. Hence, macromolecular engineering of polyphosphonates can now be envisioned by directly polymerising VPA in water.

A free N-heterocyclic carbene has been efficiently used for the organocatalysed step-growth polymerisation between aliphatic diisocyanates and diols. Both the nature of the diisocyanate monomer and the order of addition of reactants are critical parameters for the successful synthesis of soluble linear polyurethanes.