A palladium-catalysed C2-H alkynylation of benzophospholes with alkynyl bromides has been developed to afford the corresponding phosphole-alkyne conjugations in good to high yields. The C-C triple bond as well as terminal alkyne C-H bond in the obtained products is a good synthetic handle for further manipulations, thus giving the versatile π-conjugated benzophosphole derivatives. The optoelectronic properties of the newly synthesized conjugated benzophospholes are also described.