The polymerization of isobutyl vinyl ether (IBVE) and tert-butyl vinyl ether (TBVE) was carried out with metallocene and nonmetallocene catalysts, and the stereoregularity of the formed polymers was examined with C-13 NMR spectroscopy. IBVE afforded polymers with 63-68% dyad isotacticity by polymerization with mixtures of metallocene catalysts and methyl aluminoxane as a cocatalyst in toluene as a solvent. However, TBVE yielded polymers with 47-52% dyad isotacticity (21-28% triad isotacticity) under the same conditions, the isotacticity being lower than that of poly(isobutyl vinyl ether) (PIBVE). Nonmetallocene catalysts, including Ti, Zr, and Hf complexes with two phenoxy imine chelate ligands, provided PIBVE and poly(tert-butyl vinyl ether) with 63-68 and 45-51% dyad isotacticity, respectively.