A mild method for the regioselective coupling of propargyl alcohols and allylsilanes is described. The method employs an air- and moisture-tolerant rhenium-oxo complex ((dppm)ReOCl3) as a catalyst for the formation of sp3-carbon-sp3-carbon bonds without the need for prior activation of the propargyl alcohol as a halide or pseudohalide. The stability of the high oxidation state rhenium complex allows for simple reisolation and reuse of the catalyst. A broad range of functional groups is tolerated including aryl halides, olefins, esters, and acid-labile functional groups such as acetals. Furthermore, displacement of the alcohol occurs preferentially even in the presence of other electrophiles such as primary alkyl halides and conjugated esters. The use of enantiopure crotylsilanes as coupling partners allows for the asymmetric construction of two adjacent stereocenters. The potential of this reaction is demonstrated in an asymmetric synthesis of delta-lactone, di-O-methylcalopin.