We prepared Sn1−x Fe x O2 (x = 0, 0.03, 0.05, 0.10, and 1.0) nanoparticles by the polymeric precursor method based on the modified Pechini process. Two types of starting reactants for both tin and iron were explored: Sn(II)/Fe(II) and Sn(IV)/Fe(III) precursors. Thermogravimetric analysis revealed that the precursor powders prepared from Sn(IV) have higher excess in ethylene glycol in comparison to precursor samples prepared from Sn(II). XRD patterns for those samples prepared from Sn(IV) and Fe(III) were adequately fitted by introducing only the cassiterite phase of SnO2. Micro-Raman spectra also support these findings, and additionally it is found that the presence of iron broadened and reduced the intensities of the principal bands. 119Sn Mössbauer spectra indicated only the presence of Sn4+, whereas RT 57Fe Mössbauer spectra suggested the presence of two Fe3+ sites located at different distorted sites. On the other hand, micro-Raman and 57Mössbauer spectrometry showed the formation of hematite as impurity phase for those samples with iron concentrations above ~5 at.%, prepared from Fe(II) and Sn(II) precursors. In addition, their XRD patterns revealed larger average grain sizes for the cassiterite phase of SnO2 in comparison to those samples prepared from Sn(IV) and Fe(III).