Herein, we describe an effective strategy for synthesizing polythioethers with a well-defined structure through the cationic polymerization of thiirane with electron-withdrawing substituents. This strategy allows for precisely controlling the regio- and stereochemistry of the ring-opening polymerization of 2-phenylthiirane, thus allowing for producing poly(2-phenylthiirane) with high stereoregularity using enantiomeric pure thiirane.