To avoid the deleterious effects of dopant segregation, synthesis methods that facilitate a homogenous dopant distribution in the ceria lattice were employed. Though doping ceria by wet impregnation was also credited to induce a homogeneous solid solution even in the heavy regime (concentration ≥20%, A. Corma, P. Atienzar, H. Garcia and J. Chane-Ching, Nat. Mater., 2004, 3, 394–397), no follow up investigation has been reported. Herein, we investigated ceria nanoparticles (1%Tm-CeO₂ and 1%Eu-CeO₂) wet-impregnated with trivalent rare-earth (Yb, 20%), bivalent (Ca, 20%) and isovalent (Zr, 30%) metals, followed by annealing in air. Homogeneity of the solid solutions of Yb-impregnated ceria was confirmed by a two-feature characterization toolbox that included X-ray diffraction, Raman spectroscopy, transmission electron microscopy, as well as up-conversion emission as a probe tool. Since the up-conversion emission of Tm was not detectable in the absence of Yb while its efficiency depends on the average distance between Yb and Tm ions, the Yb incorporation and its migration from the surface to the lattice bulk sites in wet-impregnated ceria can be “visualized” and compared with that of the Yb bulk-doped counterpart. The use of Eu luminescence as a local probe confirmed the homogeneity of solid solutions of Ca and Zr-impregnated ceria and also sustained the opposite roles of Ca and Zr as the repeller and the scavenger of oxygen vacancies, respectively. All these results suggested that heavy doping of ceria by wet impregnation with metals with +2, +3 and +4 valencies represent a facile alternative to conventional doping approaches. Therefore, the effects of the amount and the type of metal dopant on the structural properties of CeO₂ could be investigated in a more systematic and probably a more reproducible manner, which would significantly increase the potential of ceria in catalysis and other applications.