Sequential treatment of trimethylsilylethynyl-TTF (TTFMe3) 3a dissolved in methanol with potassium fluoride, the chloro complex Cp*(dppe)FeCl (8; Cp* = η5-C5(CH3)5, dppe = 1,2-bis(diphenylphosphino)ethane) in the presence of ammonium hexafluorophosphate, and finally with KOBut provided Cp*(dppe)FeC≡C-TTFMe3 (1), which was isolated in 69% yield as an air- and moisture-sensitive orange powder. The X-ray crystal structure, IR, cyclic voltammetry (CV), UV−vis, Mossbauer, and DFT data obtained for 1 show that only weak interactions take place between the iron center and the TTFMe3 core and that the latter acts as a rather poor electron donor vis-a-vis the organometallic group. When reacted with 1.0 equiv of [(C5H5)2Fe][PF6] in tetrahydrofuran (THF) at −60 °C, 1 gives the thermally stable radical cation 1[PF6], which was isolated in a pure form as a purple powder (77%). The FeIII derivative was characterized by the same spectroscopic methods as 1 complemented by HRMS and elemental analyses also obtained for neu...