Gold-catalyzed oxidative cross-coupling of allcynes to unsymmetrical diynes has been achieved for the first time. A N,N-ligand (1,10-Phen) and PhI(OAc())2 were identified as crucial factors to promote this transformation, giving the desired cross-coupled conjugated diynes in excellent heteroselectivity (>10:1), in good to excellent yields, and with large substrate tolerability.