The effect of implanting57Fe ions on the crystal structure of Nb–Zr alloys has been studied using Mössbauer spectroscopy on57Fe nuclei and X-ray diffraction. As a result of implantation, a metastable structure was formed in the Nb–Zr alloy. The XRD data indicated a decrease in the crystal lattice parameter of niobium; that is, there was a compression of the niobium planes when implanted with iron ions. Mössbauer spectroscopy revealed three states of iron. The singlet indicated a supersaturated Nb(Fe) solid solution; the doublets characterized the diffusion migration of atomic planes and crystallization of voids. It was shown that the values of the isomer shifts in all three states did not depend on the implantation energy, which indicates the invariance of the electron density on the57Fe nuclei in the studied samples. The resonance lines of the Mössbauer spectra were significantly broadened, which is typical for materials with low crystallinity and a metastable structure that is stable at room temperature. The paper discusses the mechanism of radiation-induced and thermal transformations in the Nb–Zr alloy, which leads to the formation of a stable well-crystallized structure. A Fe2Nb intermetallic compound and the Nb(Fe) solid solution formed in its near-surface layer, while Nb(Zr) remained in the bulk.