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High‐molecular‐weight alternating and acrylate‐rich copolymers of propylene and ethyl acrylate were prepared by using boron trifluoride to complex the acrylate ester. The polymerizations were run at room temperature and autogeneous pressures with free‐radical initiation. The polymers were characterized by their nuclear magnetic resonance (NMR) and infrared (IR) spectra, differential scanning calorimetry, and gel permeation chromatography. The proton and 13C NMR spectra show that the equimolar copolymers are alternating to a high degree.