A palladium-catalysed carbon–carbon bond-forming reaction via deaminative/decarboxylative cross-coupling of organoammonium salts with carboxylic acids was developed. Under the reaction conditions, polyfluoroaromatic carboxylic acids, propiolic acids and α-cyano benzyl carboxylic acid reacted smoothly with benzyl ammonium salts to produce the corresponding carbon–carbon coupling products in good-to-excellent yields.