The pentafluoroorthotellurate (F₅TeO–, teflato) group was transferred to two organonickel precursors resulting in the formation of [Ni(Hacac)₂(OTeF₅)₂] and [Ni(ⁱᴾʳIm)₂(OTeF₅)₂]. These complexes show completely different behavior in their stability against stronger coordinating agents, coordination arrangement, and their spin state. Interestingly, traces of water did not hydrolyze the teflato ligand, instead coordinating to the central nickel atom with formation of a dinuclear complex [{Ni(Hacac)(H₂O)( OTeF₅)(μ‐OTeF₅)}₂].