Zirconium alkenyls and dienyls of E configuration, obtained by the hydrozirconation of alkynes or conjugated enynes containing a terminal triple bond undergo the Zr/Te exchange reaction by treatment with C 4 H 9 TeBr or C 4 H 9 TeI in THF at -78 °C. The Zr/Te exchange reaction proceeds with total retention of configuration and with complete stereoselectivity at the carbon 1, furnishing (E)-butyltelluro alkenes (64 - 86% yields) and (E)-1-butylteluro-1,3-dienes (68 - 75% yields). Vinylic tellurides were transformed into α,β-unsaturated esters and carboxylic acids with total retention of the regio- and stereochemistry via vinyl lithium intermediates.