The excited state properties of wheel-and-axle-type phosphorus(V) porphyrin dimers, whose central phosphorus atoms are covalently connected via an ethylenedioxy bridge, were investigated to determine the contribution of the charge transfer (CT) state. The lifetime of the excited singlet state of each dimer decreased with increasing solvent polarity. The lifetime of the symmetry-disturbed dimer, in which the redox potentials of the two porphyrin rings are differentiated by unsymmetrical axial substitution, was much shorter than that of the symmetrical dimer. The decrease in lifetime suggests the enhancement of non-radiative decay through the CT state. Similar phenomena were also observed for the quenching of the excited singlet state of porphyrin dimers possessing orthogonally oriented porphyrin rings. In addition, analogous trimers with parallel or orthogonal configurations showed stronger fluorescence quenching than that of the corresponding dimers.