The dynamics of charge recombination (CR) of ion pairs formed upon electron-transfer quenching of Zn tetraphenylporphine (ZnTPP) in the S-2 state has been investigated by fluorescence upconversion. These ion pairs have two possible CR pathways: (A) a highly exergonic CR to the neutral ground state and (B) a moderately exergonic CR leading to the formation of ZnTPP in the S-1 state. Upon addition of quencher, the S-2 fluorescence decreases considerably, while the S-1 fluorescence is unaffected, indicating unambiguously that CR occurs via path B. A large fraction of the S-2 fluorescence quenching occurs in less than 100 fs. CR to the S-1 state of ZnTPP takes place with time constants around 400 fs.