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X-ray absorption spectroscopy at Mn K - and L -edges, and at O K -edge, combined with the x-ray diffraction and magnetization measurements are performed to study the electron structure of La 0.7 Ca 0.3 Mn 1-x Sc x O 3 (x = 0.0; 0.03, and 0.05) perovskites. Substitution of manganese by scandium decreases Curie temperature, T c, and increases lattice parameters because of the different electron configuration and radii of trivalent manganese and scandium ions. The T c decrease is explained by the change of level of hybridization of O 2 p and Mn 3 d states. This is manifested by the parallel shift of O K -edge, change of intensity of 2 p 3/2 and 2 p 1/2 spectrum lines and T C with x increase. Fourier transform of the EXAFS spectra shows a change of local crystal structure caused by the larger Sc3+ than the Mn3+ ions. • Electron structure of La 0.7 Ca 0.3 Mn 1-x Sc x O 3 manganites is studied. • Change of electron hybridization of Mn 3 d and O 2 p states is observed. • Change of Mn L -edge spectra intensity and T C is parallel with x. • Shift of O K -edge and T C is parallel with x. • Fourier transform of EXAFS spectra shows a change of local crystal structure. [ABSTRACT FROM AUTHOR]