LnZrOx (Ln: La, Sm) mixed oxides of Ln: Zr = 1 were prepared by different methods (complex polymerized method, sorption of cations on starch from aqueous salt solution and conventional co-precipitation with addi-tional redispersion of precipitate by ultra sound) and calcined at 700-1300 ℃. Their specific structural features and changes were studied and discussed. Various characterization methods were used such as X-ray diffraction, Electron microscopy, Fourier-transform infrared and Raman spectroscopy, UV-Vis spectroscopy, X-Ray ab-sorption fine structure and X-ray photoelectron spectroscopy. The formation of pyrochlore structure occurred at 1100-1300 ℃ from fluorite-like pseudocubic phase ZrO2 regardless the method of preparation. This phase had a block-like structure consisting of ZrO2 nanocrystals stabilized by Ln cations and residual anions such as hydroxyls and carbonates. The desorption of such anions with heating already started at 900 ℃ and lead to local changes of Zr cations coordination to octahedral and to the formation of pyrochlore nanodomains inclusions within fluorite-like phase. The increased cation mobility and further elimination of anions caused by further heating was accompanied by the formation of bulk pyro-chlore phase at 1100-1300 ℃. Even after calcination at 1300 ℃ the local microheterogeneity as well as defects were identified at domains boundaries or sintered microstructure. These specific features of the formed pyro-chlores depend on the method of preparation.