Traditional covalent semiconductors require complex processing methods for device fabrication due to their high cohesive energies. Here, we develop a stable, ligand-free perovskite semiconductor ink that can be used to make patterned semiconductor-based optoelectronics in one step. The perovskite ink is formed via the dissolution of crystals of vacancy-ordered double perovskite Cs2TeX6 (X = Cl -, Br -, I -) in polar aprotic solvents, leading to the stabilization of isolated [TeX6] 2octahedral anions and free Cs + cations without the presence of ligands. The stabilization of the fundamental perovskite ionic octahedral building blocks in solution creates multi-functional inks with the ability to reversibly transform between the liquid ink and the solidstate perovskite crystalline system in air within minutes. These easily processable inks can be patterned onto various materials via dropcasting, stamping, and spraying or painting, highlighting the crucial role of solvated octahedral complexes towards rapid formation of phasepure perovskite structures in ambient conditions.