Treatment of organoboronic acids with hydrofluoric acid generates an in situ tetracoordinate hydronium organotrifluoroborate species which undergoes counterion exchange with tetra-n-butylammonium hydroxide. The resultant tetraalkylammonium salts are as air and moisture stable as their potassium organotrifluoroborate counterparts with the added advantage of being readily soluble in organic media. They were found to undergo Pd-catalyzed Suzuki–Miyaura cross-couplings with a variety of aryl- and alkenylhalides under mild conditions. Their Pd-catalyzed cross-coupling with acid halides is also possible for the generation of ketones.