Sulfur dioxide has a long history as a reagent for organic synthesis. For example, it is known to take part in a number of distinct pericyclic processes, it is exploited in the synthesis of aromatic sulfonyl chlorides, in co-polymerization with alkenes, and in combination with nucleophilic organometallic species to deliver sulfinate salts. Despite this varied reactivity profile, and the corresponding range of compounds that can be prepared, the number of applications of these reactions in synthesis is arguably lower than would be expected. Examples of applications of sulfur dioxide as a reagent in catalytic processes are even more scarce. This talk will demonstrate the utility of the charge transfer complex, DABCO-bis(sulfur dioxide), as a bench-stable solid reagent that can function as a sulfur dioxide surrogate in a number of processes. I will also show how use of the same charge transfer complex has allowed the development of a series of new transition metal catalyzed processes that introduce SO2-functionality. Recent results that show how the loss of SO2 can be used to generate versatile nucleophilic coupling partners for challenging cross-coupling processes will also be discussed.