The synthesis, characterization and photophysical properties of two perfluoroalkyl (5,10,15,20-tetrakis-[trifluoromethyl]- and [heptafluoropropyl]-porphyrin) and two perfluoroaryl (5,10,15,20-tetrakis-[2,6-difluorophenyl]- and [pentafluorophenyl]-porphyrin) are described, with reference to their potential in both photodynamic therapy (PDT) and in vivo imaging by fluorescence and ¹⁹F nuclear magnetic resonance spectroscopy. Absorption and fluorescence spectra, fluorescence lifetimes and triplet–singlet difference spectra are reported. Triplet yields have been obtained by flash photolysis and pulse radiolysis, whereas yields of sensitized singlet oxygen formation have been determined by time-resolved phosphorimetry. All four compounds show high yields of triplet formation and singlet oxygen sensitization. The spectral properties, stability and attractive solubility characteristics of the perfluoroalkyl derivatives make them particularly suitable candidates for future study for applications in PDT.