Time-resolved spectroscopic techniques are used to examine the photochemistry of OClO in water, alcohol, acetonitrile, toluene, and sulfuric acid solutions. In all solvents, excitation of the near-UV (2)A(2) <-- B-2(1) transition leads to two competing photochemical reactions : dissociation into OCl + O and formation of Cl + O-2. Based on orbital correlations of the isolated molecule, Cl can be formed by two distinct mechanisms, (1) direct elimination of Cl from OClO, maintaining the C-2v symmetry axis along the reaction coordinate to form Cl + O-2((1) Delta(g)), and (2) isomerization to ClOO, which thermally dissociates into Cl + O-2. Experimental evidence supporting both pathways for the condensed phase reactivity of OClO is presented, The quantum yield for direct elimination of Cl is solvent dependent. The role of ClOO in the excited state photochemistry of OClO is discussed in detail. In many of the solvents studied, a photogenerated transient farms within the instrument response that absorbs in the blue-green region of the optical spectrum. This species reveals identical kinetics to those exhibited by the UV absorption assigned to ClOO. These observations provide compelling evidence that ClOO has electronic excited state(s) similar in energy to the lowest energy states of OClO. The potential involvement of low-lying electronic states of ClOO in the photochemistry of OClO is discussed.