Previous pump-probe experiments on the OCIO molecule are analyzed and a consistent interpretation of the experimental observations is proposed. We demonstrate that a direct observation of the very weak (2)A(1) state of OCIO is possible with a proper femtosecond pulse, and suggest that it is necessary to introduce an accidental resonance of the probe pulse with the highly excited D or E states for understanding the observed distinct photodissociation dynamics of the (2)A(2) state using pump pulses of slightly different wavelengths. A transient abnormal peak, observed in the OCIO+ ion signal after a stronger excitation, is also convincingly interpreted. (C) 2004 Elsevier B.V. All rights reserved.