We report various high-energy electron spectroscopic data on sintered polycrystalline La1−xSrxMnO3and La1−xSrxCoO3withx=0.0, 0.1, 0.2, 0.3, and 0.4. The data presented consist of x-ray photoelectron transition metal 2pcore level and valence band spectra, x-ray initiated transition metalL3VVspectra, Bremsstrahlung isochromat spectra, and soft x-ray absorption spectra at the oxygenK-edge. Substitution of trivalent La with divalent Sr introduces holes into the system, driving an insulator-to-metal transition along with magnetic transitions. The spectral changes with progressive hole doping reflect the evolution of electronic structure across the phase transition.