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Supramolecular architecture named as porphyrin nanochannels (PNCs), including tetrathiafulvalene (TTF) and p-aminophenol as electron-donating guests in the inner space, was prepared with the hydrochloride salt of dodecaphenylporphyrin ([H4DPP]Cl2) by self-assembly based on intermolecular π−π interactions. The crystal structure of the TTF-included PNC (PNC−TTF) was determined by X-ray crystallography. Intermolecular π−π interaction was recognized among peripheral phenyl groups of the porphyrin, mainly in the direction of the crystallographic c axis to form a column structure. Photoinduced electron transfer from the guest molecules to [H4DPP]Cl2 occurred to give the electron-transfer state involving cation radicals of the guest molecules and one-electron reduced [H4DPP]Cl2, {[H4DPP+•]Cl2}−, via the photoexcited singlet state of [H4DPP]Cl2 in PNC. The reactions were examined by solid-state femtosecond laser flash photolysis and ESR measurements to determine the rate constants of electron transfer and electro...