The photodissociation of the strongly solvated radical O-3(-) (generating O-2 and O-) has been studied in aqueous solution by femtosecond pump-probe spectroscopy. The near-UV absorption band of O-3(-) exhibits a prompt bleach due to photolysis (390 nm excitation), which is followed by a partial recovery (3.5 ps) that is assigned to delayed geminate recombination, The transient spectrum of O-3(-) shows no evidence of excess vibrational energy content, indicating that vibrational relaxation of O-3(-) occurs on a faster time scale than the recombination process (3.5 ps). This overall picture is in strong contrast to the standard prototype for solution recombination reactions, i.e. the widely investigated photodissociation of I-2 in nonpolar solvents, For I-2, photodissociation and prompt recombination (similar to 0.3 ps) lead to hot I-2 molecules that relax on the tens of picoseconds time scale. The extremely fast vibrational relaxation and the slow recombination of O-3(-) in water apparently stem from strong solute-solvent interactions for both O-3(-) and O-. The O-3(-) behavior may in fact be a common situation for polar reactions in polar solvents. In these studies, O-3(-) was generated via a known reaction by photolysis of an oxygenated basic solution of hydrogen peroxide. The quantum yield of cage escape for O-3(-) photodissociation has been measured to be 0.50 +/- 0.02, assuming that the long-lived bleach is due entirely to cage escape. The long-lived bleach may, however, also be due to other photophysical pathways that involve long-lived, low-lying O-3(-) excited states. Both the apparent cage escape yield and recombination dynamics are identical within experimental error in H2O and D2O. The rotational reorientation time of O-3(-) has been measured to be 2.3 ps.