New coordination compounds of iron(II) sulfate, hexafluorosilicate, and perrhenate with 2,6-bis(benzimidazole-2-yl)pyridine (L), namely, [FeL2]SO4 ∙ H2O (I), [FeL2]SiF6 ∙ H2O (II), and [FeL2](ReO4)2 ∙ 1.5H2O (III) have been synthesized. The complexes have been studied by static magnetic susceptibility, electronic (diffuse reflectance), IR, and Mössbauer spectroscopy, and X-ray diffraction. The μeff(T) study of dehydrated complexes I–III (1–3) within the range 80–520 K has shown the spin transition 1А1 ⇔ 5Т2. A two-stage transition is observed in complex 1, whereas one-stage transitions occur in complexes 2 and 3. The forward spin transition temperatures (Тс↑) of complexes 1–3 are 423 and 503, 476, 362 K, respectively. Complex 3 sustains an abrupt spin transition with a hysteresis in the μeff(T) curve (ΔT = 21 K).