We have investigated the perturbed electronic properties of meso-substituted free-base porphyrins with symmetric and asymmetric arrangements of substituents using time-resolved spectroscopic measurements and theoretical calculations. The extent of electronic perturbation by substituents in meso-substituted porphyrins is mainly affected by the isoenergetic condition of frontier MOs of porphine and substituent units, nonorthogonal geometry, and geometrical arrangement of substituents. By using the asymmetric arrangements of p-aminophenyl and pentafluorophenyl substituents, we can induce the electron-rich condition on the porphine unit and the intramolecular charge transfer character in the excited state. On the basis of this work, we can gain further insight into the energetic and geometric factors of substituents, the interaction between porphine and substituent units, and the perturbed photophysical and electronic properties by substituents, which provides a firm basis for further understanding of the catalytic activities or photophysical properties of porphyrins in porphyrin-based molecular catalysts and electronics.