Starting from the alcohols ferrocenol (Fe(C 5H 5)(C 5H 4–OH), Fc–OH) and 1,1′-ferrocenediol (Fe(C 5H 4–OH) 2, fc(OH) 2), a series of new ferrocene derivatives has been prepared, in which oxygen is directly connected with the ferrocene unit. The reactions with organoelement chlorides such as Me 3SnCl, tBuPCl 2, tBu 2PCl and tBu 2AsCl lead to complexes containing the heteronuclear groups O–Sn, O–P, and O–As, respectively. The analogous trimethylsiloxy derivatives, Fc–OSiMe 3 and fc(OSiMe 3) 2, are obtained by the reaction of the lithiated ferrocenes, FcLi or fcLi 2, with bis(trimethylsilyl)peroxide, Me 3Si–OO–SiMe 3. The monofunctional ferrocenol reacts with carboxylic acid chlorides to give di- or trinuclear ferrocenol esters depending on the structure of the acid chloride. The corresponding reactions of the bifunctional 1,1′-ferrocenediol lead to either mononuclear [ n]ferrocenophanes, or dinuclear [ n. n]ferrocenophanes depending on the nature of the acid chloride. The new compounds were characterized by their 1H- and 13C-NMR spectra as well as their mass spectra. The molecular structures of diferrocenyl phthalate, o-C 6H 4(CO 2Fc) 2 and of the [6]ferrocenophane fcO 2[(CO) 2 oC 6H 4] were determined by single crystal X-ray structure analyses.