The electronic structure of the colossal magnetorcsistance perovskite manganite materials, Lao.65Pbo.35MnO3 and Lao.TSro.aMnOa, has been studied by X-ray photoemission spectroscopy (XPS). The ls core level spectra of oxygen (O(Is)) exhibit double-peak structure with asymmetric intensities characteristic for different clmmieal environments. Ab-initio calculations allow identifying source of the peaks. The higher peak in the lower binding energy is associated with ten of oxygen atoms, and the rest of oxygen atoms (two) give the weaker peak in the higher binding energy part of the XPS spectra. The weaker peak is associated only with these two oxygen atoms which are located in the lanthanum atoms plane without Sr or Pb impurities. PACS: 71.20 Dg; 79.60.-i; 75.30 Et