In this paper, the run of the decorating process of the active support, like CeO2, by the gold nanoparticles via deposition‐precipitation method has been studied. Two types of the Au/CeO2 systems with different mean particle size (but the same morphology) of the support have been investigated. It was noted that the decoration process proceeds easily only for large crystals with average size about 67 nm. Three hypotheses were tested in order to explain unsuccessful initial Au nanoparticles decoration of the cube‐like CeO2 crystals with average size about 14 nm as a support. The tests have shown that the ratio of the molar content of the chloroauric acid to the total surface area of the support (MAu/SCeO2) has a significant impact on the decorating process of CeO2 by nano‐Au. If the above ratio is too small, the thin layer of gold instead of the Au nanoparticles is formed on the support surface. In this paper, the calculations of the real surface area (from TEM/HRTEM data) were used to adjust the optimum the MAu/SCeO2 to obtain the Au/CeO2 system with the desired properties.