Abstract A facile and environmentally friendly synthetic method for a variety of symmetrical 1, 3-diyne derivatives based on the Pd/C-CuI-catalyzed homocoupling reaction of terminal alkynes has been developed. The reaction was efficiently catalyzed by the extremely low loading (0.01-0.03 mol%) of Pd/C and CuI (3 mol%) in the presence of molecular oxygen (O 2) as an oxidant without any phosphine ligands and bases.