We used photoelectron spectroscopy, the energy-selected-photoelectron photoion coincidence (ESPEPICO) method, the Auger electron photoion coincidence (AEPICO) method, and the ab initio method to study site-specific phenomena in the C:1s photoionization of 1,1,1-trifluoroethane (CF3CH3, TFEt) condensed on a Au surface. Site-specific excitation and occurrence of different chemical shifts at two carbon sites were evident in the total electron-yield spectrum and the photoelectron spectrum, and site-specific fragmentation was evident in the ESPEPICO spectrum. The fragmentation processes inferred from the ESPEPICO and AEPICO results were very different from those occurring in the vapor phase. We also studied the effect of the surface on the site-specific phenomena observed in a 2,2,2-trifluoroethanol (TFEtOH) monolayer chemisorbed on a Si(100) surface (CF3CH2OSi{substrate}). The molecular structure of TFEtOH is the same as that of TFEt except that it has a hydroxyl group substituted for one of the hydrogen atoms. Although site-specific phenomena were also observed in TFEtOH. the fragmentation process was very different from that of TFEt because of the chemisorption structure of TFEtOH on Si(100).