Two novel Ca2(UO3)(TeO3)2 (1) and K2(UO2)2O2(TeO3) (2) uranyl tellurites were obtained from telluric acid, used as a starting reagent for both compounds. In 1, the tetraoxido core is coordinated by TeO3 groups and UO4 squares polymerize into [UO3] chains. The tetraoxido core coordination modes in compound 1 are unique. New layered ⋡2[(UO2)2(TeO3)O2]2– topology is observed for 2. Both of the compounds were studied by the means of high‐temperature X‐ray diffraction. The thermal decomposition of 1 and 2 is different and leads to formation of uranate compounds.