Phosphorescent iridium(III) complexes have been attracting increasing attention in applications as luminescent chemosensors. However, no instance of an iridium(III) complex being used as a molecular logic gate has hitherto been reported. In the present study, two iridium(III) complexes, [Ir(ppy)(2)(PBT)] and [Ir(ppy)(2)(PBO)], have been synthesized (PBT, 2-(2-Hydroxyphenyl)-benzothiazole; PBO, 2-(2-hydroxyphenyl)-benzoxazole), and their chemical structures have been characterized by single-crystal X-ray analysis. Theoretical calculations and detailed studies of the photophysical and electrochemical properties of these two complexes have shown that the N boolean AND O ligands dominate their luminescence emission properties. Moreover, [Ir(ppy)(2)(PBT)], containing a sulfur atom in the N boolean AND O ligand, can serve as a highly selective chemodosimeter for Hg2+ with ratiometric and naked-eye detection, which is associated with the dissociation of the N boolean AND O ligand PBT from the complex. Furthermore, complex [Ir(ppy)(2)(PBT)] has been further developed as an AND and INHIBIT logic gate with Hg2+ and histidine as inputs.