The cationic ferrocenyl-containing complexes [(η 6 -C 6 Me 6 ) 2 Ru 2 (μ-η 1 :η 2 -CH–CHFc) 2 (μ-H)] + (3) and [(η 6 -C 6 Me 6 ) 2 Ru 2 (μ-PPh 2 )(μ-η 1 :η 2 -CH–CHFc)(μ-H)] + (4) have been synthesised in ethanol from ethynylferrocene and the dinuclear precursors [(η 6 -C 6 Me 6 ) 2 Ru 2 (μ-H) 3 ] + (1) and [(η 6 -C 6 Me 6 ) 2 Ru 2 (μ-PPh 2 )(μ-H) 2 ] + (2) respectively, and isolated as tetrafluoroborate salts. The spectroscopic data of 3 and 4 as well as the single-crystal X-ray diffraction analysis of [4][BF 4 ] show that the alkyne function of ethynylferrocene has been converted to a σ/π-ethenyl ligand by transfer of a bridging hydride from the diruthenium backbone onto the α-carbon of the triple bond in ethynylferrocene. The ferrocenyl-containing diruthenium compounds [3][BF 4 ] and [4][BF 4 ] as well as their parent compounds [1][BF 4 ] and [2][BF 4 ] have been studied by voltammetric techniques: Whereas 1 shows only an irreversible Ru(II)/Ru(III) oxidation, the phosphido-bridged derivative 2 displays two well-separated one-electron redox processes. In the case of 3 and 4, the ferrocenyl substituents give rise to additional reversible ferrocene/ferrocenium waves.