An investigation of the variation of hole concentration within the CuO2 planes using X-ray absorption near-edge structure (XANES) spectroscopy with synchrotron radiation in the (Bi2−xPbx)Sr2CaCu2Oy [(Bi,Pb)-2212]series of high-Tc superconductors synthesized by solid state reaction in air is presented. Pb is found to have the valence of 2+ in the samples of this series. Moreover, the hole concentration increases with increasing Pb content. The results lead us to conclude that the substitution of Pb2+ in the Bi3+ sites of the (Bi,Pb)-2212 system causes the compounds to be in the over-doped state. This effect results in the compounds having a high critical current density.