Reaction of iron(II) thiocyanate with an excess of trans-1,2-bis(4-pyridyl)-ethylene (bpe) in acetonitrile at room temperature leads to the formation of (1), which is isotypic to its Co(II) analogue. Using slightly different reaction conditions the literature known compound (2) was obtained as a phase pure material. Simultaneous differential thermoanalysis and thermogravimetry prove that the hydrate 2 transforms into the anhydrate (3), that decomposes on further heating into the new ligand-deficient 1:1 compound of composition (4), which can also be obtained directly by thermal decomposition of 1. Further investigations reveal that 4 can also be prepared under solvothermal conditions, and single crystal structure analysis shows that the iron(II) cations are linked via -1,3 bridging thiocyanato anions into chains, that are further connected into layers by the bpe ligands. Magnetic measurements, performed on powder samples, prove that 1 and 2 show only Curie–Weiss behavior, whereas in 4 antiferromagnetic ordering with a Néel temperature of 5.0 K is observed. At T < 4.0 K a two-step metamagnetic transition occurs at applied magnetic fields of 1300 and 1775 Oe. The magnetic properties are discussed and compared with those of related compounds.