New iron(II) coordination compounds with 2,6-bis(4,5-dimethyl-1H-imidazol-2-yl)pyridine (L) and closo-borate(2–) anions [FeL2]B10H10⋅2H2O and [FeL2]B12H12⋅H2O have been synthesized. The compounds have been identified and studied by CHN analysis, electron spectroscopy (diffuse reflection spectroscopy), IR, Mössbauer, and EXAFS spectroscopies, X-ray powder diffraction, and static magnetic susceptibility. The structures of the coordination knots of complexes [FeL2]B10H10⋅2H2O and [FeL2]B12H12⋅H2O has been obtained by modeling the EXAFS spectra. The ligand is coordinated by the iron(II) ion in a tridentate-cyclic manner by two nitrogen atoms of imidazole cycles and a nitrogen atom of pyridine to form the FeN6 coordination knot. The study of the temperature dependence of the magnetic susceptibility in the range of 80–500 K has showed that the high-temperature spin-crossover 1А1 ↔ 5Т2 manifests itself in the obtained compounds.