In BaTiO the phase transition from tetragonal to cubic is connected with the disappearance of the ferroelectric polarization. In photoelectron spectroscopy huge transient shifts in the binding energies of all core-level photoemission lines have been observed while heating and cooling through the Curie temperature. Excitation energies from 2 keV to 6 keV have been used to show this to be a bulk effect and not a surface effect alone. These observations are discussed in terms of charging, which results from the disappearance of the ferroelectric polarization. This mechanism has previously been proposed as the origin of electron emission in ferroelectric materials. Besides the jump-like shifts, additional permanent shifts in binding energies have been observed for the tetragonal and the cubic phase. These experimental shifts have been related to theoretical ones from ab initio calculations. In addition to BaTiO single crystals, systems with CoFeO and NiFeO overlayers on BaTiO have been investigated. The low conductivity of these layers sets them apart from metallic overlayers like Fe or Co, where the shifts are suppressed. This difference adds further support for charging as the origin of the effect.