A two step, totally stereoselective synthesis of (E,E)-1,4-dialkoxy-1,3-butadienes from chiral secondary alcohols has been developed. The key step involves the regio- and stereoselective hydrozirconation of alkoxyethynes derived from chiral alcohols; the intermediate (E)-(2-alkoxyvinyl)zirconium compounds, after treatment with cuprous chloride and thermally induced decomposition of the corresponding (2-alkoxyvinyl)copper, give the dialkoxybutadienes in moderate yield but with complete (E,E) diastereoselectivity.