The reaction of anhydrous FeCl2 with 2‐(4′,4′‐dimethyloxazolin‐2′‐yl)thiophenolate (ox‐phS–) afforded mononuclear [Fe(ox‐phS)2] (A) and binuclear [{FeIII(ox‐phS)}2(μ‐S)2] (B). In B, iron(III) and S2– resulted from an unexpected redox reaction involving elemental sulfur and the iron(II) starting material. Complexes A and B co‐crystallise reproducibly in a 2:1 proportion. An attempt to prepare (oxazolinylthiophenolato)iron(III) from Li(ox‐phS) and anhydrous FeCl3 in the presence of N,N,N′,N′‐tetramethylethane‐1,2‐diamine (tmen) gave another redox reaction with disulfide D, bis{2‐(4′,4′‐dimethyloxazolin‐2′‐yl)phenyl}disulfide (ox‐phS‐Sph‐ox), and trans‐[FeCl2(tmen)2] (E) as 1:1 co‐crystallised products. Characterisation of all complexes included Mössbauer spectroscopy and single‐crystal X‐ray diffraction analysis. Quantum mechanical (TDDFT) calculations for A and cyclic voltammetry experiments carried out with A and C helped to distinguish between ligand‐ and metal‐based electronic transitions and redox processes. Results add to the knowledge of the rich redox chemistry of early transition metals with soft S‐donor ligands, with possible consequences for catalytic and biochemical transformations.