The work aims to prepare nanostructured La2(Zr0.75Ce0.25)2O7 spherical feedstocks for thermal sprayed ultra-high temperature with nanopowder granulation technology, and then fabricate nanostructured thermal barrier coatings with thermal spraying method to meet the service temperature requirements of the next-generation thermal barrier coatings. The La2(Zr0.75Ce0.25)2O7 nanopowders synthesized by chemical co-precipitation were used as raw materials to prepare nanostructured La2(Zr0.75Ce0.25)2O7 feedstock by ball milling, spray drying and heat treatment. The nanostructured La2(Zr0.75Ce0.25)2O7 thermal barrier coatings were prepared by atmospheric plasma spraying. Microstructure and morphologies of original nanopowders, nanostructured feedstocks and as-sprayed coating were analyzed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In addition, the composition of nanostructured feedstocks was analyzed by inductively coupled plasma-atomic emission spectrometry (ICP-AES). The as-prepared nanostructured La2(Zr0.75Ce0.25)2O7 feedstocks were spherical with smooth surface. The composition of feedstocks was basically consistent with stoichiometric ratio. Compared with the original nanopowders, the grain growth of feedstocks was not significant. Some grains of as-sprayed coatings grew up, but the nanostructure still remained. Therefore, the nanostructured La2(Zr0.75Ce0.25)2O7 spherical feedstocks and nanostructured thermal barrier coatings have been successfully prepared, which are expected to be the next-generation ultra-high temperature thermal barrier coatings.