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Eu3+/Tb3+ co-doped nanocomposite containing CeO2 nanocrystals was successfully prepared by an in situ sol–gel polymerization approach. High-resolution transmission electron microscopy demonstrated the homogeneous precipitation of CeO2 nanocrystals among the polymethylmethacrylate (PMMA) matrix. The thermal stability and UV-shielding capability of the obtained nanocomposite were improved with increase of CeO2 content. The tuning of the emissive color from green and yellow to red can be easily achieved by varying the dopant species and concentration. These results suggested that the obtained nanocomposite could be potentially applicable in transparent solid-state luminescent devices.