Palladium/copper-cocatalyzed cross-coupling reactions of alkynylsilanes with aryl tosylates or mesylates afforded the corresponding unsymmetrical diarylethynes in moderate to good yields. The optimized reaction conditions to afford higher yields of cross-coupled products were found to be 5 mol % of [PdCl2(bpy)], 15 mol % of BrettPhos, and 10 mol % of (CuCl)-Cl-I in DMF as a solvent.