X-ray photoemission spectroscopy (XPS) of Cu 1− x Tl x Ba 2Ca 2Cu 3O 10− δ (Cu 1− x Tl x -1223) superconductors thin films is studied. These films were prepared by amorphous phase epitaxy method on the SrTiO 3 substrate. This compound has Cu 1− x Tl x Ba 2O 4− δ charge reservoir layer and three CuO 2 planes. The atoms in the CuO 2 planes have strong covalent bonding, while the some of the atoms in Cu 1− x Tl x Ba 2O 4− δ charge reservoir, such as oxygen (O δ ) have predominantly secondary bonding and could be removed from the unit cell. The deliberate or inadvertent removal of the oxygen from the unit cell may change the charge state of the constituent atoms in the charge reservoir layer. The charge state of the atoms in the unit cell, ultimately determine the carriers concentration, the shape of the Fermi surface and hence control the mechanism of superconductivity. The doping via charge reservoir layer of Cu 1− x Tl x -1223 films had been carried out by post-annealing of the samples in the N 2 atmosphere at 650 °C. It was observed that the critical temperature of thin films increases with the post-annealing at this temperature. In the present studies we have carried out XPS experiments to under stand the mechanism to the microscopic level. It is observed from these studies that before annealing the thallium in Cu 1− x Tl x -1223 superconductor thin films was in Tl 3+ oxidation state, which changes its oxidation state from Tl 3+ to Tl 2+ and Tl 1+. The changed oxidation state of the thallium increases the density of the carriers in the CuO 2 planes, which increases their Fermi-vector K F and hence their Fermi-velocity v F. These parameters in turn increase the critical temperature of the material. In the present studies the T c( R = 0) has increased from below 77 K to 92 K with post-annealing in nitrogen atmosphere.