The radio‐iodination of arenes is investigated from organosilane and organogermane precursors using ipso‐electrophilic halogenation (IEH). Discovery of a mild base mediated process allows radio‐iodination in HFIP (1,1,1,3,3,3‐hexafluoro‐2‐propanol) of either aryl silane or germane, with germanes being more reactive. Clinical potential of arylgermanes as radio‐iodination precursors is demonstrated through the labelling of [125I]IMTO (iodometomidate) and [125I]MIBG (meta‐iodobenzylguanidine) thus offering an alternative to radio‐iododestannylation processes using non‐toxic precursors. [ABSTRACT FROM AUTHOR]