Photoinduced processes of a series of phosphorus tetraphenylporphyrin (PTPP) derivatives ([PTPP-(NHC6H4X)2]+Cl-, X = OCH3, CH3, H, Cl, CF3, and CN) have been investigated by using femtosecond laser flash photolysis mainly. PTPP with OH as an axial ligand showed S2 fluorescence upon excitation of the Soret band. The S2 fluorescence lifetime was estimated to be 1.5 ps. On the other hand, both S2 and S1 fluorescence bands of PTPP-(NHC6H4X)2 were difficult to observe, indicating the existence of an additional deactivation process such as charge separation (CS). From MO calculation and cyclic voltammetry, PTPP and the axial ligand are expected to act as an acceptor and a donor, respectively, upon excitation of PTPP. CS via the S2 state was confirmed during the femtosecond laser flash photolysis by observing the transient absorption of radical anion of PTPP. Furthermore, CS via the S1 state of PTPP was also observed. The CS rate via the S1 state was faster than that from the S2 state. The free energy dependence of the electron-transfer rates was discussed on the basis of Marcus theory.