A series of porphyrin-based ionic complexes were prepared through the reaction of two porphyrin precursors, 5,10,15,20-tetrakis(4-(2-pyridyl)phenyl)porphyrin H2TPhPyP (1) and trans-dihydroxo [5,10,15,20-tetrakis(4-(2-pyridyl)phenyl)porphyrinato]tin(IV) Sn(OH)2TPhPyP (2), with various acids (HCl, HNO3, CF3COOH, H2SO4, H2CO3, and H3PO4). The complexes were characterized via elemental analysis, 1H nuclear magnetic resonance spectroscopy, electrospray ionization mass spectrometry, Fourier transform infrared (FT-IR) spectroscopy, ultraviolet (UV)-visible spectroscopy, fluorescence spectroscopy, and field-emission scanning electron microscopy (FE-SEM). Each compound exhibited different results for UV-visible, fluorescence, FT-IR, and FE-SEM studies depending on the counter anions. The complexes possessed different self-assembled nanostructures based on electronic interactions between the cations of compounds 1 and 2 with different counter anions. These aggregated species are stabilized by electrostatic forces and the π-π stacking interactions between the two porphyrin rings, in which the counter anions play an important bridging role. The counter anions also play an important role in controlling the morphology and photocatalytic properties of the as-developed materials. The complexes were then used for the photocatalytic degradation of the malachite green (MG) dye in aqueous media under visible light irradiation for up to 70 min. A morphology-dependent photocatalytic degradation of the MG dye was observed for all the ionic complexes, with efficiencies ranging from 50% to 95%.