Photodissociation at 266 nm of some protonated peptides was investigated using a tandem-TOF spectrometer equipped with a cell near its first time focal point where the laser was irradiated. When a high voltage was applied to the cell, each product ion peak split into several components with different flight times. One of these was due to in-cell direct formation of the product ion and another due to post-cell formation. Those in between were due to consecutive dissociations, the first steps of which occurred inside the cell and the second steps outside the cell. A method based on flight time calculation was developed to analyze these components and to identify the intermediate ion for each consecutive component. The technique allows time-resolved photodissociation mechanistic studies on a 100-ns timescale.