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The extended x-ray absorption fine structure (EXAFS) recorded from tin-doped α-Fe2O3, prepared by the mechanical milling of tin dioxide and α-Fe2O3 and by the hydrothermal processing of iron- and tin-containing precipitates, can be interpreted in terms of a model in which tin occupies both substitutional octahedral sites and the interstitial octahedral sites in the corundum-related α-Fe2O3 structure. The EXAFS and 119Sn Mössbauer spectra suggest that structural models derived from x-ray powder diffraction data do not adequately describe the complexity of the local environment of tin in α-Fe2O3. In particular, the EXAFS and 119Sn Mössbauer spectra recorded from materials made by mechanical milling show evidence of more disorder. The 119Sn Mössbauer spectra also indicate that the degree of order in the materials made by both methods is far from perfect and that the microstructural defects are highly sensitive to tin content and the preparative method.