Unsymmetrical E- and Z-stilbenes can be synthesized from two differently substituted benzaldehydes in a MesP(TMS)Li-promoted reductive coupling sequence. Depending on the order of addition of the two coupling partners, the same olefin can be produced in either E- or Z-enriched form under identical reaction conditions. A systematic study of the correlation between the stereochemical outcome of the reaction and the substitution pattern at the two aldehydes is presented. The results can be used as guidelines to predict the product stereochemistry.