Dissociative photoionization of CF3I is studied in the region of the CF3I+ A state (13–15 eV). We observe a pronounced anisotropy of the I+ fragment ions in the time of flight coincidence spectra obtained at 14.24 and 15.0 eV photon energy, but having the same 13.3 eV parent ion internal energy. It is the result of a strong alignment in the photoionization process at these energies, probably related to a specific autoionization process. A new and lower value of 13.40±0.05 eV is measured for the appearance potential of the CF2I+ fragment.