Detailed studies of core-electron profiles in the high-energy photoelectron spectra of TCNQ and eighteen of its complexes have been carried out. In all these solids, satellites appear 2 to 4 eV on the higher-binding energy side of both the N1s and C1s main peaks. The satellites are attributable to a shake-up process involving intramolecular transitions between the π-electron valence molecular orbitals in both neutral and ionic TCNQ species. Except in a few cases, which are discussed, intermolecular (charge-transfer) interaction plays a minor role in the core-level, photoelectron spectra of the complexes. Valence band measurements of some of the complexes, the temperature-dependence of some N1s profiles as well as the splitting of some of the metal ion core-levels, are also briefly discussed.