This review highlights recent progress in the synthesis and application of vinyl ethers (VEs) as monomers for modern homo- and co-polymerization processes. VEs can be easily prepared using a number of traditional synthetic protocols including a more sustainable and straightforward manner by reacting gaseous acetylene or calcium carbide with alcohols. The remarkably tunable chemistry of VEs allows designing and obtaining polymers with well-defined structures and controllable properties. Both VE homopolymerization and copolymerization systems are considered, and specific emphasis is given to the novel initiating systems and to the methods of stereocontrol.