A number of organometallic stilbenes of the general type [Co(η 4 -C 4 Ph 4 )(η 5 -C 5 H 4 CHCHR] are reported where R is C 6 H 4 X-4 (X = H, OMe, Br, NO 2 ), 1-naphthyl, 9-anthryl, 1-pyrenyl, (η 5 -C 5 H 4 )Co(η 4 -C 4 Ph 4 ), and (η 5 -C 5 H 4 )Fe(η 5 -C 5 H 4 Y) {Y=CHO, CHC(CN) 2 and CHCHC 5 H 4 -η 5 )Co(η 4 -C 4 Ph 4 )}. They were prepared by Wittig or Horner–Wadsworth–Emmons reactions which yield both E and Z or only E products respectively. The isomers were separated and all compounds characterised by standard spectroscopic techniques as well as by X-ray diffraction methods in many cases. The electrochemistry of the stilbene analogues in dichloromethane solution is also reported. In most, the (η 5 -C 5 H 4 )Co(η 4 -C 4 Ph 4 ) functional group undergoes a reversible one-electron oxidation. For those molecules that also include (η 5 -C 5 H 4 )Fe(η 5 -C 5 H 4 Y), this is preceded by the reversible oxidation of the ferrocenyl group. Spectroscopic and structural data suggests that for most compounds there is little electronic interaction between Co(η 4 -C 4 Ph 4 )(η 5 -C 5 H 4 ) and the R end groups which are effectively independent of one another. The only exceptions to this are Z and E-[Co(η 4 -C 4 Ph 4 )(η 5 -C 5 H 4 CHCHC 6 H 4 NO 2 -4], and [Co(η 4 -C 4 Ph 4 )(η 5 -C 5 H 4 CHCHC 5 H 4 -η 5 )Fe{η 5 -C 5 H 4 CHC(CN) 2 }] where the electronic spectra are respectively consistent with a significant Co(η 4 -C 4 Ph 4 )(η 5 -C 5 H 4 )/NO 2 donor/acceptor interaction and a less significant Co(η 4 -C 4 Ph 4 )(η 5 -C 5 H 4 )/C(CN) 2 one. However, OTTLE studies show that in the electronic spectra of [Co(η 4 -C 4 Ph 4 )(η 5 -C 5 H 4 CHCHR] + there are low energy absorption bands (950–1800 nm) which are attributed to R→Co(η 4 -C 4 Ph 4 )(η 5 -C 5 H 4 ) + or, when R is a ferrocenyl-base group, Co(η 4 -C 4 Ph 4 )(η 5 -C 5 H 4 )→(η 5 -C 5 H 4 )Fe(η 5 -C 5 H 4 Y) + charge transfer transitions. The ferrocenyl compounds undergo cis/trans isomerisation on the OTTLE experiment timescale.