Abstract：An efficient route to skipped enynes or diynes under Cu(Ⅰ) Catalysis and solid-liquid phase transfer condition was described. The effects of reaction temperature, time, reactants, catalysts were described. We selected the best reacting condition by using the method of orthogonal experiment. This condition has the advantage of mild conditions, less amounts of catalysts, high yield and having no isomeric by-product. Eleven 1,4-diynes and enynes were synthesized in this way in good yield.