The reaction dynamics of ClO- in water following femtosecond ultraviolet photolysis is investigated by measuring time-resolved absorption and anisotropy. Ab initio calculations show that Light absorption induces charge shifting from the O- atom to the Ci atom. Molecular dynamics simulations predict that the charge shift is followed by the destruction of the solvent structure around the O atom and its formation around newly formed negative charge on the Cl atom. An ultrafast (similar to 60 fs) transient absorption change is observed and likely corresponds to the inertial part of the destruction of the solvent structure around the newly formed neutral O atom of the excited state OCl-. The early time anisotropy of -0.13 +/- 0.05 decays on the 230 fs time scale and is attributed to the dissociation along a new reaction path toward Cl + O- that is seen independently through the evaluation of the spectrum of Cl. The remaining anisotropy decays within 6 ps due to rotational diffusion of the ion. Probe wavelength dependence of the longer time dynamics (1.3-7 ps) is proposed to be the vibrational relaxation of the vibrationally hot ground state of ClO-, the generation of which can be described as electron transfer from the excited state OCl- to the ground state ClO-.