The arylation of heteroatom nucleophiles is a central strategy to reach diarylated compounds that are key building blocks in agrochemicals, materials and pharmaceuticals. Nucleophilic aromatic substitution is a classical tool for such arylations, and hypervalent iodine-mediated arylations are modern alternatives to achieve a wider scope of products. Herein, we combine the benefits of those strategies to enable an atom-efficient and transition metal-free functionalization of N- and O- nucleophiles with two structurally different aryl groups, to provide di- and triarylamines and diaryl ethers in one single step (> 100 examples). The core of this strategy is the unique reactivity discovered with certain fluorinated diaryliodonium salts, which unveils novel reaction pathways in hypervalent iodine chemistry. The method is suitable for aliphatic amines, anilines, ammonia and even water and tolerates a wide variety of functional and protecting groups. Furthermore, the retained iodine substituent is easily accessible for derivatization of the products.