AbstractThe synthesis and characterization of a series of metallocenylphosphanes of the type PR2Mc/Se=PR2Mc [Mc = Fc = Fe(η5‐C5H4)(η5‐C5H5), R = C6H5 (3a/4a), 2‐MeC6H4 (3b/4b), c‐C4H3O (3c/4c), tBu (3d/4d), c‐C6H11 (3e/4e); Mc = Rc = Ru(η5‐C5H4)(η5‐C5H5), R = C6H5 (6a/7a), 2‐MeC6H4 (6b/7b), c‐C4H3O (6c/7c), c‐C6H11 (6d/7d)] and their palladium complexes [PdCl2(PR2Mc)2] [Mc = Fc, R = C6H5 (9a), 2‐MeC6H4 (9b), c‐C4H3O (9c), tBu (9d), c‐C6H11 (9e); Mc = Rc, R = C6H5 (10a), 2‐MeC6H4 (10b), c‐C4H3O (10c), c‐C6H11 (10d)] is reported. The solid‐state structure of 4b confirms the tetrahedrally distorted geometry at phosphorus with the o‐tolyl groups indicating steric congestion, which is confirmed by 1H and 13C{1H} NMR spectroscopy. Phosphanes 3, 4, and 9 were characterized by cyclic voltammetry with [N(nBu)4][B(C6F5)4] as the supporting electrolyte. In general, the first oxidation occurs at the phosphane metallocenyl unit(s), although the appropriate Pd complexes are oxidized at more positive potentials. Depending on the phosphane or selenophosphane, follow‐up reactions occur, which are discussed. In contrast, the palladium complexes show reversible redox behavior. UV/Vis/NIR spectroelectrochemical studies carried out on 9b indicate an electrostatic interaction between the two terminal ferrocenyl groups. All of the palladium complexes were examined as catalysts in Heck and Suzuki C–C cross‐coupling and showed high catalytic activities. These results can be correlated to the electronic (1J) parameters of the selenophosphanes.