Porphyrins are acknowledged for their efficacy as photosensitizers and show potential for the treatment of water contaminated with diverse dyes. This research emphasizes the use of meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) as a photosensitizer for purifying water contaminated with rhodamine B. Investigations were conducted under homogeneous conditions using visible light irradiation, revealing the efficacy of the porphyrin in the decolorization of rhodamine B strongly depends on pH of the solution. This study demonstrated that within 120 min, the decolorization process rapidly removed about 95% of RhB at an initial pH of 3.0, while at pH 6.0, the removal rate was significantly lower, at only 12%. An extensive photophysical study of the TPPS was carried out at pH 6.0 and pH 3.0 including absorption and fluorescence spectra, fluorescence quantum yields, triplet absorption spectra, triplet lifetimes, triplet and singlet oxygen quantum yields in order to explain difference in the efficiency of RhB discoloration. A thorough investigation into mechanism revealed that neither reactive oxygen species nor singlet oxygen played a role in RhB decolorization within this system. Instead, the predominant route was found to be the electron transfer from photoexcited TPPS to RhB, followed by proton transfer at pH 3.0, leading to the generation of a colorless leuco form.