Aryl and alkenyl sulfonyl chlorides can be used in Heck-Mizoroki-type couplings with mono- and disubstituted olefins in a nitrile-functionalized ionic liquid, viz. [C3CNpy][Tf2N]. Advan­tages over previously reported methods include: (1) use of a cheap catalyst source, PdCl2, (2) ability to handle the catalyst in air, (3) ­reduced reaction times, (4) elimination of phase-transfer catalysts due to the high solubility of the inorganic base in the ionic liquid, and (5) facile recycling of the ionic liquid-palladium catalyst. The yields of coupling products remain in the same range as the reactions conducted in organic solvents. Palladium nanoparticles, characterized using transmission electron microscopy, have been identified in the ionic liquid following the Heck-Mizoroki type ­coupling reactions.