The preparation, electrical conductivity, magnetic moments, infrared, reflectance, and 57Fe Mössbauer spectra of tris(2,2,2‐trichloroethoxy) iron(III) and its adducts with some oxygen and nitrogen donor ligands are reported. Cryoscopic data of the parent compound and its complex with ethylacetate suggest these compounds to be dimeric in nitrobenzene and benzene respectively. All the compounds are covalent with FeIII having distorted octahedral arrangement which is achieved through alkoxy bridging. The magnetic moments are lesser than those required for the spin only value indicating antiferromagnetic interactions in FeIII atoms. The Mössbauer spectra are explained in terms of two FeIII high spin sites corresponding to trans‐ and cis‐positions in the structure.