XPS and NEXAFS spectroscopy were used to study calcium copper titanates (CCTO) solid solutions doped with iron and nickel atoms. The CCTO compound spectra analysis shows that titanium atoms have +4 charge state, and copper and calcium atoms - +2, and their valency does not change when doped with iron and nickel atoms at the concentration of the latter up to 6 atomic percent. In this case, doping atoms are mainly embedded into the positions of titanium atoms and have Fe 3+ and Ni 2,5+ charge states.