The carbon 1s photoelectron spectrum of CF4 measured at photon energies from 330 to 1500 eV shows significant contributions from nonsymmetric vibrational modes. These increase linearly as the photon energy increases. The excitation of these modes, which is not predicted in the usual Franck-Condon point of view, arises from the recoil momentum imparted to the carbon atom in the ionization process. A theory is presented for quantitative prediction of the recoil effect; the predictions of this theory are in agreement to the measurements. The experiments also yield the vibrational frequencies of the symmetric and asymmetric stretching modes in core-ionized CF4, the change in CF bond length upon ionization, -0.61 pm, and the Lorentzian linewidth of the carbon 1s hole, 67 meV.