A number of naphthalene derivatives containing adamantanamine binding moiety and an (CH2)n (n = 2, 3, 4, 5, 6) spacer were prepared as electron donor. A supramolecular assembly was fabricated by the inclusion complexation of the donor substrates with the host molecules,mono-6-O-p-nitrobenzoyl-β-cyclodextrin (p-NBCD) and mono-6-O-m-nitrobenzoyl-β-cyclodextrin (m-NBCD), in water. The fluorescence quenching in these systems was studied and detailed Stern-Volmer constants were measured. It revealed that an efficient photoinduced electron transfers (PET) between the naphthalene donors and the cyclodextrin acceptors occurred.