The complexes trans‐[Pt(C≡CFc)2(PFcmnBu3–m)2] (Fc = ferrocenyl; m = 0, 9a; m = 1, 9b; m = 2, 9c) were prepared by the reactions of PFcmnBu3–m (m = 0, 3a; m = 1, 3b; m = 2, 3c) with cis‐[PtCl2(SEt2)2] (6) to form [PtCl2(PFcmnBu3–m)2] (m = 0, 7a; m = 1, 7b; m = 2, 7c), which on treatment with [CuC≡CFc] (8) produced 9a–9c. The reactions of PFcmnBu3–m (m = 1–3; m = 3, 3d) with S8 or Se gave (S=)PFcmnBu3–m (m = 1, 4b; m = 2, 4c; m = 3, 4d) and (Se=)PFcmnBu3–m (m = 1, 5b; m = 2, 5c; m = 3, 5d). Compounds 5d, 7b, 7c, 9b, and 9c were structurally characterized by single‐crystal X‐ray diffraction studies; a trans arrangement of the phosphine units at the Pt center is typical. The redox behavior of 3, 4, 7, and 9 was investigated by cyclic and square‐wave voltammetry. The Fc units of 9a–9c could be oxidized separately indicating electronic interactions between the Fc/Fc+ groups of the FcC≡C units [ΔE°′ = 105 (9a), 115 (9b), 120 mV (9c)]. Cationic [9b]+ and [9c]+ exhibit weak intervalence charge‐transfer (IVCT) absorptions at = 6700 cm–1.