By means of a complex of powder X-ray diffraction techniques the features of the structural organization of highly dispersed copper-cerium CuO-CeO2 catalysts prepared by the Pechini method are studied. The current structural technique for studying nanomaterials, namely the atomic pair (interatomic distances) distribution function analysis, is used to refine the phase composition of materials with revealing highly dispersed compounds, sizes of atomic ordering regions, and possible defects. It is shown that materials synthesized from polymeric precursors represent mixed CuO-CeO2 oxides with a high concentration of structural defects. Highly dispersed individual copper compounds are not detected. The results obtained support the previous assumptions that copper cations can incorporate into the structure of cerium dioxide in the composition of copper-cerium catalysts.