An alternative route to synthesise alkenes, based only on the KO t Bu/DMF promoted activation and direct coupling of alcohols with phenyl acetonitriles, is reported. Various E-stilbenes have thus been obtained directly from alcohols that are sustainable sources of carbon, which to our knowledge, is unprecedented in the absence of transition metal based catalysts. A variation allowing, through a Csp 3 À Csp 3 bond formation, the selective synthesis of N-Heteroarenes is also described. A mechanism for the olefination pathway proceeding via an original activation of alcohols under alkyl formates is provided.