Three cationic Ir(III) complexes, 1, 2, and 3, were successfully synthesized and characterized by tuning the position of a phenyl group at the pyridyl moiety in 2-phenylpyridine. All three complexes exhibited typical aggregation-induced phosphorescence emission (AIPE) properties in CH3CN/H2O. The AIPE property was further utilized to achieve the highly sensitive detection of 2,4,6-trinitrophenol (TNP) in aqueous media with low limit of detection (LOD) values of 164, 176, and 331 nM, respectively. This suggests that the different positions of the phenyl group influence the effectiveness of 1, 2, and 3 in the detection of TNP. In addition, 1, 2, and 3 showed superior selectivity and anti-interference properties for the detection of TNP and were observed to have the potential to be used to detect TNP in practical applications. The changes in the luminescence lifetime and UV-Vis absorption spectra of 1, 2, and 3 before and after the addition of TNP indicate that the corresponding quenching process is a combination of static and dynamic quenching. Additionally, the proton nuclear magnetic resonance spectra and results of spectral studies show that the detection mechanism is photo-induced electron transfer (PET).