XPS core level and valence band spectra are presented for chemically etched epitaxial thin films of superconducting TlBa2CaCu2O7−δ, one of which is as-grown overdoped (superconducting transition temperature [Tc] = 74.5 K) and two which are annealed (Tc= 86.5 K and 87.5 K). The core levels measured from the annealed films are shifted to higher binding energies relative to those from the as-grown overdoped film, consistent with a doping-induced change in the chemical potential.