Despite the wide application of ceria-zirconia based materials in Three Way Catalysts (TWCs), Solid Oxides Fuel Cells (SOFCs), and H-2 production and purification reactions, an active debate is still open on the correlation between their structure and redox/catalytic performances. Existing reports support the need of either (i) a homogeneous solid solution or (ii) materials with nanoscale heterogeneity to obtain high activity and stability. Here we report on a simple and inexpensive approach to solve this problem taking advantage of the luminescence properties of Eu(III), used as a structural probe introduced either in the bulk or on the surface of the samples. In this way, the real structure of ceria-zirconia materials can be revealed even for amorphous high surface area samples. Formation of small domains is observed in catalytically important metastable samples which appear homogeneous by conventional XRD.