Photoabsorption cross-sections of CF2CH2 were measured in the carbon K-edge region and linear time-of-flight mass spectra were acquired at some photon energies across the two pi* peaks. The kinetic energy distributions of CH2+ and CF2+ with two components were deduced from the analysis of the mass spectra. The CH2+ ion with high kinetic energies increases with the extent of vibrational excitation of the C-F 1s -> pi* state, indicating that molecular vibrations play an important role in the photofragmentation of the inner-shell excited molecule. (c) 2005 Elsevier B.V. All rights reserved.