Pd-catalyzed coupling of 1,3-dienyldibromides with triarylbismuths was demonstrated for the synthesis of a diverse range of 1,3-enynes. This study provided easy access to a range of functionalized 1,3-enynes in high yields utilizing triarylbismuths in sub-stoichiometric amounts. A new and concise route was unveiled for the synthesis of extended π-conjugated molecular systems with the help of chemoselective couplings and in conjunction with Sonogashira, Heck and arylation reactions under combined catalysis.