We present a catalytic protocol utilizing bismuth for the synthesis of aromatic fluorinated thiosulfones, showcasing a seminal example of aryl silicon nucleophiles in Bi catalysis. This catalytic process is enabled by a series of Bi-based organometallic transformations, including an unprecedented transmetalation of aryl silicates to Bi(III) complexes and the formal migratory insertion of sulfur dioxide (SO2) into the Bi‒C bond. The protocol is compatible with a wide range of anionic and neutral Ar‒Si compounds, including heterocycles. Stoichiometric investigations of individual organometallic steps provide strong evidence supporting a Bi-redox-neutral catalytic cycle.