Acetylenic thiophens, ArC⋮CR (Ar = 2,2′-bithienyl-5-yl or 2-thienyl), have been prepared by a metal-catalysed Grignard coupling reaction, either from ArMgl and BrC⋮CR or from Arl and BrMgC⋮CR; the second method gave the better results. Some side-reactions are discussed.