A process for the synthesis of linear α,ω-diolefins from an allylic substrate comprises the steps of a) forming the bis-Grignard reagent XMgCH2(CH2)nCH2MgX from an α,ω-acyclic dihalide with X being a halogen; b) preparing a solution comprising an allylic substrate and a copper catalyst; c) catalyzing a coupling reaction by adding to the solution of step (b) the bis-Grignard reagent of step (a); and d) isolating and purifying the α,ω-olefin coupling reaction product.