A series of "wheel-and-axle-type" phosphorus(V) porphyrin dimers, whose central phosphorus atoms are connected to each other by various lengths of the alkyldioxy bridge, were synthesized and investigated on their excited state for the evaluation of the contribution of a charge-transfer (CT) state. The decrease of the lifetime of the singlet excited state of the dimer in the polar solvent suggest the enhancement of the nonradiative decay through the CT state. The lifetime of the symmetry-disturbed dimer was shorter than those of symmetric dimers.