A palladium-catalysed, silver-assisted regioselective C2-H alkenylation of benzophospholes with terminal alkenes has been developed. The palladium catalysis accommodates styrenes and electron-deficient alkenes including ester, ketone, nitrile, and phosphonate. Thus, this protocol enables the rapid construction of various benzophosphole-vinylene conjugations from the two simple C-H starting substrates. Optical properties of newly synthesized C2-alkenylated benzophospholes are also investigated.