1,2-Dithiooxalate (dto) can be employed as a bridging ligand and it exhibits symmetric (O,S-chelation) or asymmetric (O,O- and S,S-chelation) coordination forms. In this study, we prepared a novel dto-bridged diiron(II) complex, [{Fe(TPA)}2(μ-dto)](ClO4)2 (1), where TPA is tris(2-pyridylmethyl)amine. Interestingly, the bridging dto ligand exhibited not only the asymmetric form but also a linkage isomer and a diastereomer within the same crystal. Notably, the three isomers of 1 exhibited different magnetic properties, resulting in a multi-step spin crossover behaviour.