The effect of chain transfer agents (CTAs) ethyl acetate (EA), octyl acetate (OA), and isopropyl alcohol (IPA) on the rate of polymerization of vinylidene fluoride (VDF) in an emulsion polymerization and in solution polymerization in dimethyl carbonate (DMC) initiated by tert-butyl peroxypivalate was investigated. Pressure profiles of the polymerizations were recorded. Solids content and rate of polymerization were calculated by gravimetry; size exclusion chromatography was utilized to evaluate CTA activity, and the produced polymer microstructures were characterized by H-1 and F-19 NMR spectroscopies. It is proposed that the observed reduction in polymerization rate in both systems is due to degradative chain transfer reactions.