AbstractContrary to some published reports, the vinyl esters of saturated fatty acids polymerize readily and rapidly. Vinyl oleate, when present in excess of 5%, and oxygen exert marked retarding effects.Techniques are described for the free‐radical‐initiated polymerization of the vinyl esters of caprylic, capric, lauric, myristic, palmitic, and stearic acids in bulk, dispersion, solution, and emulsion. Some data are given for polymerization in the presence of chain‐transfer agents, such as carbon tetrachloride, dodecylmercaptan, and ethylbenzene. Conditions are reported for obtaining degrees of polymerization from about 2 (when chain‐transfer agents are employed) to 10,000 (weight average). The weight average degree of polymerization increases markedly as the conversion increases, particularly above 80%. Even up to extremely high conversions, soluble polymers are obtained in most cases.Solubility characteristics, transition point data, molecular weights (osmometric and light‐scattering), and isolation and purification techniques are also