The effect on the electrochemical oxidation and reduction potentials of 5,10,15,20-tetrakis(benzo-15-crown-5)porphyrin (TCP) and its metal derivatives (MTCP; M = Mg(II), VO(IV), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Ag(II)) upon potassium ion induced dimerization of the porphyrins was systematically performed in benzonitrile containing 0.1 M (TBA)CIO4 by differential pulse voltammetry technique. The HOMO-LUMO energy level diagram constructed from the electrochemical data revealed destabilization of the HOMO level and stabilization of the LUMO level upon dimer formation while such a perturbation was larger for the HOMO level than the LUMO level. The geometry and electronic structure of a representative ZnTCP and its dimer, K-4(ZnTCP)(2), were evaluated by the ab initio B3LYP method utilizing a mixed basis set of 3-21 G(*) for Zn, K, O, and N and STO-3G for C and H. The inter-porphyrin ring distance of the dimer calculated from the optimized geometry agreed with the spectroscopically determined one, and the calculated HOMO and LUMO frontier orbitals revealed delocalization on both of the porphyrins rings. The metal-metal distances calculated from the triplet ESR spectra of the K+ induced porphyrin dimers bearing paramagnetic metal ions in the cavity followed the trend Cu-Cu < VO-VO < Ag-Ag. However, the spectral shifts resulting from the exciton coupling of the interacting porphyrin pi-systems revealed no specific trend with respect to the metal ion in the porphyrin cavity. Additionally, linear trends in the electrochemically measured HOMO-LUMO gap and the energy corresponding to the most intense visible band of both MTCP and K-4(MTCP)(2) were observed. A reduced HOMO-LUMO gap predicted for the dimer by B3LYP/(3-21G(*), STO-3G) calculations was confirmed by the results of optical absorption and electrochemical studies.