Sulfonyl fluorides have emerged as powerful “click” electrophiles to access sulfonylated derivatives. Yet, they are relatively inert towards C−C bond forming transformations, notably under transition-metal catalysis. Here, we describe conditions under which aryl sulfonyl fluorides act as electrophiles for the Pd-catalyzed Suzuki–Miyaura cross-coupling. This desulfonative cross-coupling occurs selectively in the absence of base and, unusually, even in the presence of strong acids. Divergent one-step syntheses of two analogues of bioactive compounds showcase the expanded reactivity of sulfonyl fluorides to encompass both S−Nu and C−C bond formation. Mechanistic experiments and DFT calculations suggest oxidative addition occurs at the C−S bond followed by desulfonation to form a Pd-F intermediate that facilitates transmetalation. © 2021 Wiley-VCH GmbH