Hypervalent iodine compounds have been studied extensively in the past. They are considered to be non-toxic and mild oxidants which represent useful alternatives to toxic heavy-metal based reagents.[1] Hypervalent iodine(III) and iodine(V) species such as (diacetoxy)iodobenzene (PIDA) and the Dess-Martin periodinane are commercially available and routinely employed in oxidation reactions.[2] For synthesis of both iodine(III) and iodine(V) species, electrochemical approaches have been developed.[3] The electrochemistry of diaryl iodonium salts (see Figure, compound 3), however, is much less explored. Such compounds are typically employed as versatile arylation reagents.[4] Their conventional synthesis starts from a iodoarene that undergoes a reaction with a chemical oxidizer, followed by subsequent treatment with aryl-boron, aryl-silicon or aryl-tin reagents to yield the diaryl iodonium salt.[4] A more practical approach that does not require activated arenes is based on the use of meta-chloroperbenzoic acid (mCPBA) in presence of a strong acid (e.g. triflic acid) for oxidative C-I coupling.[5] Using electric current as an oxidizer constitutes a further advancement for synthesis of diaryl iodonium salts. In a recent example, the electrolytic transformation of iodoarenes has been carried out in a HFIP-MeCN solvent mixture using excess triflic acid as the supporting electrolyte and anion source, rendering aryliodonium triflates in medium to high yields.[6] However, the dependence on the hazardous and costly HFIP and triflic acid still represents a major limitation. In this work, the development of a cheaper, greener, and acid-free synthesis of diaryl iodonium salts is presented.[7] The method uses MeCN as the sole solvent as well as lithium salts as supporting electrolyte/anion source. Since many lithium salts with weakly coordinating anions are commercially available and well soluble in MeCN, the approach provides flexibility regarding the choice of the anion.[1] a) A. Yoshimura, V. V. Zhdankin, Chem. Rev. 2016, 116, 3328-3435; b) B. Olofsson, I. Marek, Z. Rappoport, PATAI's Chemistry of Functional Groups, John Wiley & Sons, 2018.[2] a) C. H. Willgerodt, J. Prakt. Chem. 1886, 33, 154-160; b) D. B. Dess, J. C. Martin, J. Org. Chem. 1983, 48, 4155-4156.[3] a) R. Francke, Curr. Opin. Electrochem. 2019, 15, 83-88; b) R. Francke, Curr. Opin. Electrochem. 2021, 28 [4] E. A. Merritt, B. Olofsson, Angew. Chem. Int. Ed. 2009, 48, 9052-9070.[5] M. Bielawski, M. Zhu, B. Olofsson, Adv. Synth. Catal. 2007, 349, 2610-2618.[6] M. Elsherbini, W. J. Moran, Org. Biomol. Chem. 2021, 19, 4706-4711.[7] A. Scherkus, B. H. Müller, R. Francke, 2023; manuscript in preparation. Figure 1