The multi-photon dissociative photoionization dynamics of CF3I has been studied with femtosecond two-color pump-probe time-of-flight mass spectra at a pump pulse of 265 nm and a probe pulse of 398 nn. This enables the A band and 5ppi(3)7ssigma((2)Pi(1/2)) Rydberg state to be accessed with the pump beam. The observed fast and slow decay components of CF3+ and I+ reflect the fast repulsive A band and some higher lying ion-pair states may be responsible for the decay of the 5ppi(3)7ssigma((2)Pi(1/2)) Rydberg state. The results provide information on the different multi-photon pathways producing these ions and the de-excitation mechanism of the 5ppi(3)7ssigma((2)Pi(1/2)) Rydberg state. (C) 2003 Elsevier Science B.V. All rights reserved.