The present invention relates to synthetic polymers having high molecular weight and low polydispersities, and methods of synthesis thereof. One embodiment of the present invention provides a method of polymerizing that includes dissolving acrylate monomers in a fluid media having an olefin-containing polyalcohol amide surfactant; and initiating a polymerization reaction of the acrylate monomers with a polymerization initiator to produce a polymer having a molecular weight of at least about 500,000 and a polydispersity index of about 1.25 or less.