In this report, we have demonstrated the synthesis of surfactant-assisted different morphologies of meso-tetra(4-carboxyphenyl)porphyrin assemblies (spherical to flower shaped). These nano/micro assemblies are well characterized by scanning electron microscopy and X-ray diffraction. The formation of assemblies is driven by noncovalent interactions such as hydrophobic-hydrophobic and aromatic π-π stacking between the molecules. The steady state and time-resolved spectroscopic investigation reveal that different assemblies are formed by virtue of special supramolecular organizations. The photocatalytic activities of different assemblies have been demonstrated with an organic pollutant Rhodamine B dye under the visible light irradiation. Such porphyrin based assemblies could pave the way for designing new optical based materials for the applications in photocatalytic, photovoltaic, and light harvesting system.