Acetylenic tellurides react with Cp 2 Zr(H)Cl in THF at room temperature to give the α-zirconated vinyl telluride intermediates 39, which react with a wide range of electrophiles to give several types of trisubstituted olefins, such as α-halo vinyl tellurides, ketene telluro(seleno) acetals, ketene telluro acetals, and vinylic tellurides of Z configuration. Acetylenic selenides undergo similar reactions, but a lack of regioselectivity results in the formation of a mixture of α-zirconated 19 and ss-zirconated 20 vinylic selenide intermediates. After a detailed study was established that the use of 2.0 equivalents of Cp 2 Zr(H)Cl is crucial to perform the total hydrozirconation of acetylenic selenides or tellurides.