A variety of chiral and achiral zirconocene complexes were investigated for the stereoselective dehydrogenative coupling of phenylsilane. Polymerization of PhSiH3 with rac-(EBI)ZrCl2/BuLi or Cp2Zr(H)Cl yields a stereoregular polymer by Si-29 NMR spectroscopy. These results suggest that the stereogenic centers of the growing polymer chain may play a role in the stereochemistry of phenylsilane polymerization. A syndiotactic microstructure for the polyphenylsilanes is tentatively assigned on the basis of comparisons of their Si-29 NMR chemical shifts with those of known stereoregular cyclic oligomers.