The electronic relaxation and photodetachment dynamics of an electron originating from an aqueous iodide ion have been studied using femtosecond absorption spectroscopy. The results indicate the importance of an upper excited charge transfer to solvent (CTTS) state, of odd parity, in the potential well of the solvated ion. The upper excited CTTS state, which is accessed by two-photon excitation, relaxes in < 50 fs to the lowest excited CTTS, which in turn relaxes to the ground state of the I- in 80 fs. It is found that most of the solvated electrons are produced by a three-photon excitation to a photoionized state, rather than from the CTTS excitation.