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Thin films of an iron–tellurium alloy were prepared by rf sputtering and characterized by means of x‐ray diffraction and Mössbauer spectroscopy. In an immiscible range in equilibrium composition, tellurium atoms were incorporated into iron, distorting the lattice to some extent. Beyond 14 at. % of Te, an amorphous structure appeared. Judging from the metastable superstructures formed at higher substrate temperatures and the covalent nature in the bonding, the kinetic hindrance against the redistribution of the elements due to the local atomic forces during rapid quenching plays a critical role in the formation of amorphous structure in this alloy. In addition, beyond some intermetallic range around 60 at. % Te, an amorphous phase also exists in the tellurium‐rich region. The thermal stability was examined by a differential scanning calorimetry; the electrical resistivity is also discussed.