Samples of CaCu₃Ti_4-4хNi_4хO_12-δ. were obtained by solid phase synthesis method. X-ray diagrams of all preparations show trace amounts of the impurity phase of copper oxide(II), at x≥0.04 the impurity CaTiO₃ reflexes are shown. Admixtures of nickel-containing phases in samples in all investigated concentration interval by methods RFA and electronic scanning microscopy are not fixed. It is established that the polarization processes in the samples are carried out at different speeds by two mechanisms. As a result of modeling using two equivalent schemes, it was found that the homogeneity of samples with growth x decreases, in the sample CaCu₃Ti_4-4хNi_4хO_12-δ (х=0.03) polarization proceeds three times faster than in x=0.06. The sample CaCu₃Ti_3.88Ni_0.12O_12-δ conducts direct electric current better and polarizes faster in a variable electric field than x=0.06. The activation energy of the samples is practically the same: 0.491 (x=0.03) and 0.499 eV (x=0.06). After 350 °С the homogeneity of the material deteriorates, which indicates a possible disorder of the structure or a break in the chemical bonds.