The pairing of ions of opposite charge is a central principle of chemistry. Even though the ability to intercalate anions is desirable for many applications, it remains a key challenge for numerous host materials with their outmost layers beingn anions. In this work, we introduce a hydrothermal ion-exchange synthesis to intercalate oxidative S and Se anions between the Se layers of FeSe, which leads to single crystals of novel compounds (Se/S)(x)(NH3)(v)Fe2Se2. In particular, the unusual anion-anion bonding between the intercalated S (or Se) and Se layers exhibits strong ionic characteristics. The charge transfer through the Se layer to S (or Se) intercalants is further confirmed by the elevated oxidation state of Fe ions and the dominant hole carriers in the intercalated compounds. By intercalating S, for the first time superconductivity emerged in hole-doped iron chalcogenides. The generality of this chemical approach was further demonstrated with layered FeS and NiSe. Our findings thus open an avenue to exploring diverse aspects of anionic intercalation in similar materials.