<p>Copolymers of fluoroethylene and vinyl ethers (FEVE) are soluble and curable at relatively low temperature, and are used as high-performance coatings and paints. Currently, most market-available FEVE products obtained through solution polymerization contain a large fraction of organic solvent, and hence, volatile organic compound (VOC) emissions cause environmental issues. In this study, the emulsion copolymerization of chlorotrifluoroethylene (CTFE) and vinyl ethers using an environmentally friendly emulsification system to produce waterborne FEVE was investigated. In addition to mixed nonionic and ionic surfactants, macromolecular monomer with double bond and polyoxyethylene segments were used in the emulsification system. The effect of adding macromolecular monomer and polyoxyethylene segment length of the nonionic surfactant on emulsion copolymerization were analyzed. An optimized emulsifier system for FEVE is proposed, and the prepared FEVE latexes exhibit excellent storage stability and film formation ability.</p>