Mechanical alloying method was applied to prepare nanocrystalline iron-based Fe1−xZnx solid solutions with x in the range 0.01 ≤ x ≤ 0.05. The structural properties of the materials were investigated with the Mössbauer spectroscopy by measuring the room temperature spectra of 57Fe for as-obtained and annealed samples. The spectra were analyzed in terms of parameters of their components related to unlike surroundings of the iron probes, determined by different numbers of zinc atoms existing in the neighborhood of iron atoms. The obtained results gave clear evidence that after annealing process, the distribution of impurity atoms in the first coordination spheres of 57Fe nuclei is not random and it cannot be described by binomial distribution. The estimated, positive values of the short-range order parameters suggest clustering tendencies of Zn atoms in the Fe-Zn alloys with low zinc concentration. The results were compared with corresponding data derived from Calphad calculation and resulting from the cellular atomic model of alloys by Miedema.