In this work, we investigated the effects of counter anions, P-substituents, and solvents on the optical and photophysical properties of 2-phenylbenzo[b]phospholium salts in solution. A series of 2-phenylbenzo[b]phospholium salts was prepared by P-alkylation or P-phenylation of 1,2-diphenylbenzo[b]phosphole followed by anion exchange reactions. X-ray crystallographic analyses of six benzo[b]phospholium salts showed that each phosphorus center has an onium nature with an essentially tetrahedral geometry. 1H NMR and steady-state UV-vis absorption and fluorescence spectroscopic measurements of these phospholium salts revealed the pivotal role of counter-anion solvation. The observed results are discussed on the basis of the association-dissociation equilibrium between a contact ion pair (CIP) and a solvent-separated ion pair (SSIP) in solution. The hexafluorophosphates exist as SSIPs and emit intense fluorescence, irrespective of the P-substituents and solvents. In contrast, the iodides are present as SSIPs in methanol but exist as equilibrium mixtures of the two emitting species, SSIP and CIP, in dichloromethane. As a consequence, fluorescence intensities of the iodides varied significantly depending on the solvents, P-substituents, and solution concentrations. These findings were studied in more detail using time-resolved fluorescence spectroscopy and fluorescence titration measurements. The light-emitting properties of the 2-phenylbenzo[b]phospholium halides in the CIPs rely on heavy atom effects derived from the counter halide anions on the S1 state of the adjacent cationic benzo[b]phosphole π-systems. The present study suggests that 2-arylbenzo[b]phospholium salts would be promising scaffolds for developing new phosphole-based ionic fluorophores that are capable of responding to external stimuli such as anionic species and solvents.