Dichloro[(2-dimethylamino)propyldiphenylphosphine]palladium (PdCl2(alaphos)) was found to be much more effective as catalyst than other palladium complexes for cross-coupling of aryl triflates with alkynyl Grignard reagents. Reaction of bromoaryl triflates with alkynyl Grignard reagents in the presence of PdCl2(alaphos) catalyst gave high yields of alkynyl arene bromides, which were formed by selective replacement of triflate by alkynyl group.