Fe2TeO6 (FTO), an antiferromagnetic magnetoelectric material which crystallizes in tetragonal (P42/mnm, 136) crystal structure, shows close to room temperature interesting magnetic interactions. To understand the complexity in its magnetism, a huge variation in its magnetic properties has been reported by various groups, which have been attributed to the presence of Fe2O3 (an impure phase) in the final FTO compound. Herein, synthesis using alternate ingredients and Synchrotron structural investigation of single phasic FTO are presented. Out of the several initial ingredients (Fe2O3, Fe3O4 with TeO2, Te(OH)6) in solid state reaction route, only the reaction between Fe3O4 and TeO2 results in the single phasic FTO (not reported so far), while the others (Fe2O3 with TeO2 or Te(OH)6) result in certain amount of Fe2O3 impurity. Rietveld refinement on Synchrotron X-ray Diffraction data and Fe K edge Extended X-ray Absorption Fine Structure data provide the overall similarity between the average crystalline structure and local structure of FTO, indicating the intrinsic nature of it’s complex magnetic behavior. Copyright © 2017 VBRI Press.