Highly enantio-enriched (E)-allylsilanes were synthesized by palladium-catalyzed intramolecular bis-silylation of chiral allyl alcohols and subsequent Peterson-type elimination with organolithium reagents. The enantiomeric excesses of the allylsilanes were determined after hydroboration with 9-BBN followed by oxidation, revealing remarkably high stereospecificity for the present synthesis.