Terminal alkynes undergo oxidative-coupling smoothly in the presence of the CuCl-TMEDA catalytic system in hydrophobic [bmim] PF6 ionic liquid under aerobic conditions to produce 1, 3-diynes in excellent yields under mild conditions. The substrates, alkynes, show enhanced reactivity and selectivity in ionic liquids (ILs). The recovery of the catalyst is facilitated by the hydrophobic nature of the [bmim] PF6 ionic liquid.