In conclusion, we have developed a strategy for the synthesis of iodo-embedded diaryl sulfides from iodonium salts in the absence of transition metals, external bases and thiols. Aryl groups containing acid or base sensitive substituents, as well as sterically congested substituents could be transferred to S-nucleophiles under mild reaction conditions. The applicability of the diarylation was demonstrated using heteroaryl and drug-derived iodonium salts, outlining a route to the corresponding sulfides in excellent yields. A novel type of difunctionalization strategy was discovered using aryl(vinyl)iodonium salts, whereby aryl(vinyl) sulfides could be obtained in excellent stereoselectivity through a sequential arylation and vinylation. The developed difunctionalization was amenable to one-pot transition metal free reduction to reach thioanilines and a potential drug candidate derivative. A mechanistic proposal is given, substantiated by DFT studies and isolation of the key intermediate. Overall, a general synthetic methodology harnessing the reactivity of iodonium salts has been presented that enables further applications.