The fluorinated tris-thiolate compounds Ln(SC6F5)(3) can be isolated as THF, pyridine, or DME coordination complexes. In THF, the larger Ce forms dimeric [(THF)(3)Ce(SC6F5)(3)](2) (1) with bridging thiolate ligands, while the smaller lanthanides (Ln = Ho (2), Er (3)) form monometallic (THF)(3)Ln(SC6F5)(3) compounds. There is a tendency for fluoride to coordinate to Ln throughout the lanthanide series (Ce-Er). The cerium compound 1 contains a pair of bridging thiolates connecting two eight-coordinate Ce(III) ions. Of the two terminal thiolates, only one exhibits a distinct Ce-F bond. In contrast, the Ho derivative (THF)(3)Ho(SC6F5)(3) is a molecular compound in the solid state, with two monodentate thiolates and one thiolate that again coordinates through both S and F atoms. Incorporation of a stronger Lewis base reduces but does not necessarily eliminate the tendency to form Ln-F bonds. Structural characterization of the eight-coordinate (pyridine)(4)SM(SC6F5)(3) (4) reveals a single, clearly defined Ln-F interaction, while in (pyridine)(4)Yb(SC6F5)(3) (5) there are no Yb-F bonds. In the structure of (DME)(2)Er(SC6F5)(3) (6) the DME ligands completely displace F from the Er coordination sphere.