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To determine favorable conditions for preparation of syndiotactic polymers, various factors which influence the stereoregulation of vinyl esters were studied. In bulk polymerizations, vinyl esters having bulky substituents or polar substituents were found most suitable for the syndiotactic polymerization. Tri‐n‐butylborane and azobisisobutylonitrile showed some difference in stereoregulation, the magnitude of the difference being dependent on the type of vinyl ester used. Solvents were found to have a significant effect on stereoregulation. Some gave higher syndiotacticity than bulk and some gave lower syndiotacticity.