Four fatty acid vinyl esters were synthesized by transesterification between vinyl acetate and lauric acid, myristic acid, palmitic acid, stearic acid, respectively. Fatty acid vinyl ester oligomers were prepared from polymerization of four fatty acid vinyl esters in the presence of potassium persulfate in methanol. The α-sulfonation of these four fatty acid vinyl ester oligomer were carried by direct addition of sulfur trioxide. Especially, molecular weights of sodium α-sulfo fatty acid vinyl ester oligomers were measured by boiling point method.