In an effort to use clean technologies, fatty acid methyl esters (FAME) produced from canola have been used as a polymerization solvent. Solution polymerizations of four commercially important monomers have been studied using FAME as a solvent. A series of methyl methacrylate (MMA), styrene (Sty), butyl acrylate (BA) and vinyl acetate (VAc) homopolymerizations in FAME were carried out at 60 °C at different solvent concentrations. Chain transfer to solvent rate constants were obtained using the Mayo method. The transfer constants increased in the order: MMA < Sty < BA < VAc. Under the conditions studied, the MMA solution polymerization in FAME was observed to behave as a precipitation polymerization. The estimated chain transfer to solvent rate constants were employed in a polymerization simulator to predict the polymerization rates and average molecular weights.