We report ultraviolet photoemission spectra and spectra of the spin polarization (SSP) of photoemitted electrons from La1−x Pb x MnO3 for photon energies hω<11 eV and X‐ray photoemission density of states using monochromatized AlKα radiation. Contributions from high spin Mn3+ and Mn4+ ions to the photocurrent are unambiguously identified in the binding energy range O=EF<EB<3.5 eV, while the bonding levels generated by the covalent admixture of O(2p) and Mn(3d) states are located between 3 and 7 below EF, overlapping with Pb(6s) levels. We compare these results with the predictions of thw two limiting models for the description of outer d‐electrons in perovskite, the ligant field approach and the generalized LCAO interpolation scheme of Mattheiss. From the structure in the SSP we deduce that the correlation energy Ueff of 3d‐electrons in these ionic ferromagnets cannote exceed 2‐2.5 eV.