The electron photoemission spectra of valence bands and core-level states of manganese perovskite La0.67Pb0.33(Mn1−xFex)O3 with x = 0, 0.01, 0.03, 0.06, 0.10 and 0.15 were measured by the X-ray and Ultraviolet Photoemission Spectroscopy (XPS and UPS) below and above the metal-insulator transition. From analysis of the Mn 2p core-level spectra the ratio Mn 3+ /Mn 4+ was calculated as a function of the iron content. Comparison of the valence band spectrum with band structure calculations and with the high-resolution spectra measured at synchrotron radiation for Ca-, Ba-and Ce-substituted manganites revealed the strong hybridisation of Mn 3d and of O 2p states between −3 eV and −7 eV, and no estimated oxygen states between 0 eV and −2 eV where the Mn-3d states play a predominant role. The composition dependent insulating energy gaps were measured at room temperature. Reasons for the behaviour were discussed taking into account previous analysis of XPS/UPS spectra of other manganese perovskites.