The accurate determination of structure and thermal expansion of refractory materials at temperatures above 1500 degrees C is challenging. Here, for the first time, we demonstrate the ability to reliably refine the structure and thermal expansion coefficient of oxides at temperatures to 2200 degrees C using in situ synchrotron diffraction coupled with aerodynamic levitation. Solid solutions in the Eu2O3-ZrO2 binary system were investigated, including the high-temperature order-disorder transformation in Eu2Zr2O7. The disordered fluorite phase is found to be stable above 1900 degrees C, and a reversible phase transition to the pyrochlore phase is noticed during cooling. Site occupancies in Eu2Zr2O7 show a gradual increase in disorder on both cation and anion sublattices with increasing temperature. The thermal expansion coefficients of all cubic solid solutions are relatively similar, falling in the range 8.6-12.0x10(-6)C(-1). These studies open new vistas for in situ exploration of complex structural changes in high-temperature materials.