The synthesis and characterization of a series of large porphyrin oligomers are important not only for elucidation of the energy and/or the electron transfer functions of the photosynthetic reaction centre but also for application of the functions to molecular architecture. In this paper, we report the systematic synthesis of novel "wheel-and-axle-type" phosphorus(V) porphyrin oligomers, whose porphyrin rings are separated by various lengths of stable axial bridge(s) connected with the central phosphorus atoms. Additionally, for the construction of large molecular systems containing multiple redox centres, systematization of donor-photosensitizer-acceptor triad molecules into large molecular systems is accomplished by electrochemical polymerization, where the polymer will be directly deposited on the terminal electrode. As an application of the polymer, a layered cell composed of polybithiophene and the porphyrin polymers was constructed.