The intermolecular three-component coupling of aryl or vinyl halides, diarylacetylenes, and monosubstituted alkenes effectively proceeds in the presence of palladium acetate, lithium chloride, and sodium bicarbonate as catalyst, promoter, and base, respectively, in aqueous DMF or DMSO to produce the corresponding 1,3-butadiene or 1,3,5-hexatriene derivatives. Use of dienyl bromides allows the coupling to afford 1,3,5,7-octatetraenes. Under the present catalytic conditions, fulvene derivatives are also formed efficiently by the 1:2 coupling of vinyl bromides and diarylacetylenes without adding the alkenes.