The S-2 state properties of Sb-tetraphenylporphyrin (SbTPP) derivatives were investigated using subpicosecond spectroscopic methods. The S-2 fluorescence of various SbTPP derivatives was observed for the first time. It was revealed that the S-2 fluorescence lifetime changed depending on the donor-ability of the ligand because of the contribution of the charge separation to the S-2 excited SbTPP, which was confirmed by transient absorption spectroscopy.