Molecular-frame photoelectron angular distributions (MFPADs) for CF4 in the fluorine K-shell ionization region have been measured at three photon energies 705, 725 and 775 eV. The molecular axis was defined by the momenta of the F+-CF3+ ions detected in coincidence. The MFPADs were compared with ab initio calculations using the time dependent density functional theory. The results of a calculation assuming a localized F ls core-hole agree better with the observed MFPADs than the results of a calculation using a delocalized core-hole, especially for 775 eV. (C) 2007 Elsevier B.V. All rights reserved.