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Nanosized and highly reactive Mg4Ta2O9 were successfully synthesized by aqueous sol–gel method compared with conventional solid-state method. Ta-Mg-citric acid solution was first formed and then evaporated resulting in a dry gel for calcination in the temperature ranging from 600°C to 800°C for crystallization in oxygen atmosphere. The crystallization process from the gel to crystalline Mg4Ta2O9 was identified by thermal analysis and phase evolution of powders was studied using X-ray diffraction (XRD) technique during calcinations. Particle size and morphology were examined by transmission electron microscopy (TEM) and high resolution scanning electron microscopy (HR-SEM). The results revealed that sol–gel process showed great advantages over conventional solid-state method and Mg4Ta2O9 nanopowders with the size of 20–30 nm were obtained at 800°C.