New iron(II) complexes with 2,6-bis(1H-imidazol-2-yl)-4-methoxypyridine (L) of the composition [FeL2]An∙mH2O (A = SO42−, n = 1, m = 2 (I); A = ReO4−, n = 2, m = 1 (II); A = Br−, n = 2, m = 2 (III)) have been synthesized and investigated. To determine the coordination ability of the ligand, a single crystal of a copper(II) complex of the composition [CuLCl2] (IV) was obtained and studied by X-ray technique. CompoundsI–IIIwere studied using methods of X-ray phase analysis, electron (diffuse reflection spectra), infrared and Mössbauer spectroscopy, static magnetic susceptibility. The study of the µeff(T) dependence showed that the1A1↔5T2spin crossover manifests itself in the compounds. The spin crossover is accompanied by thermochromism: there is a distinct color change orange ↔ red-violet.