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X-ray photoelectron spectroscopy was used to identify the oxidation states of ions in La1 – xCaxCr1 – yMyO3 (M = Mn, Fe, Ni, Cu) perovskite oxides, to determine the surface composition of the samples, and to assess the effect of B-site substitutions on the electronic spectrum of the chromites. The binding energies of the La 4d, Ca 2p, Mn 2p, Ni 2p, Cr 2p, and O 1s core levels were determined, and the effect of the dopant on the shape of the La 4d and O 1s peaks was analyzed.