The pale-green, air-sensitive complex [(Me3Si)2N]2Fe(μ-Cl)Li(THF)3 was synthesized serendipitously by the reaction of iron(II) chloride in THF with 1 equiv of KN(SiMe3)2 and subsequent addition of CpLi and was structurally characterized by X-ray diffraction. ClLi(THF)3 acts as a ligand and appears to be a better donor than THF for the three-coordinate trigonal-planar Fe atom.