Phosphorescent sensors are essential for rapid visual sensing of volatile acids, due to their profound impact on ecosystems and human health. However, solid phosphorescent materials for acid-base stimulus response are still rare, and it is important to achieve real-time monitoring of volatile acids. In order to obtain an efficient and rapid response to volatile acid stimulation, N-H and -NH2 substituents are introduced into an auxiliary ligand to synthesize a new cationic Ir(III) complex (Ir-NH). The AIE property of Ir-NH leads to enhanced emission in the aggregated state, which facilitates the construction of solid-state acid-base sensors. More importantly, due to the introduction of -NH2 and N-H in the molecular structure, reversible switching of the emission color of Ir-NH under acid-base stimulation was successfully achieved. A convenient and efficient sensing device for volatile acid monitoring was prepared using Ir-NH as the active material. Our results provide a new strategy for designing phosphorescent materials with AIE and acid-base stimulus-responsive properties.