<p>Chromium-containing solid solutions CaCu₃Ti_{4 – 4<i>x</i>}Cr_4<i>x</i>O_12–δ (space group <i>Im3</i>) were synthesized by the solid-state method. The unit cell parameters vary slightly, from 7.3897 Å (<i>x</i> = 0.02) to 7.3866 Å (<i>x</i> = 0.06). Copper oxide is detected in the intergranular space of all samples. The ceramics exhibit a low-porosity grain microstructure. Scanning electron microscopy (SEM) indicates that an increase in the chromium content (<i>x</i> = 0.01 – 0.06) leads to a reduction in the maximum longitudinal crystallite size from 16 to 10 μm. The charge states of cations in chromium-doped calcium copper titanate CaCu₃Ti₄O₁₂ (CCTO) were investigated using x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure spectroscopy (NEXAFS). Spectroscopic data confirm that titanium cations exhibit a +(4 – δ) charge state, while copper and calcium cations are in the +2 state and chromium cations in the +3 state.</p>