Sn(IV)-protoporphyrin IX (Sn-Pp) in aqueous media exists as a mixture of monomeric and dimeric species, which can be readily distinguished on the basis of their absorption maxima at around 410 and 386 nm respectively. Sn-Pp dimers prevail as the pH is decreased and are characterized by a lower fluorescence quantum yield, a larger tendency to undergo photobleaching and a reduced photosensitizing efficiency compared with the Sn-Pp monomer. The photosensitizing action of Sn-Pp appears to involve the intermediacy of singlet oxygen (O2)-O-1, as shown by photo-oxidation studies with N-acetyl-tryptophanamide in light and deuterated water solutions. Using 1,3-diphenyl-isobenzofuran as a substrate, the quantum yield of (O2)-O-1 generation by monomeric Sn-Pp was found to be about 0.6.