A set of SubPc-Porphyrin dyads and triads have been synthesized by the nucleophilic substitution reaction of hydroxyl-containing meso-substituted porphyrins and a good electron acceptor, dodecafluorosubphthalocyanine. Acid-catalyzed condensation of p-hydroxybenzaldehyde and the corresponding dipyrromethane, followed by zinc metallation, afforded the appropriate metalloporphyrins. Subsequent nucleophilic substitution occurred between the porphyrin and the axial chlorine atom of the subphthalocyanine when reacted in a sealed tube at 180 °C. The structures of all the synthesized compounds were characterized by 1H NMR, 13C NMR and mass spectroscopy. The photophysical and electrochemical studies have also been performed by using UV–Vis, fluorescence spectroscopy and cyclic voltammetry experiments.