E-1-Ferrocenyl-4,4-dimethylpent-2-ene-1-one has been synthesised from the Friedel–Crafts acylation of ferrocene with E-3- tert-butylacryloylchloride and converted to 1-ferrocenyl-3-chloro-4,4-dimethylpentan-1-one using ethereal hydrogen chloride. This new chloro ketone has been converted into three new ferrocene alcohols: 1-ferrocenyl-3,4-dimethyl-4-hydroxypentan-1-one, 1-ferrocenyl-3-chloro-4,4-dimethylpentan-1-ol, and 2,2,6,6-tetramethyl-3-ferrocenyl-5-chloroheptan-3-ol. A new dinuclear ferrocene derivative, E, E-2,2,9,9-tetramethyl-5,6-diferrocenyl-deca-3,7-diene, was isolated after treatment of 1-ferrocenyl-3-chloro-4,4-dimethylpentan-1-ol with acidic alumina; its structure was confirmed by X-ray crystallography, whilst electrochemistry revealed metal–metal interactions of similar magnitude to those seen for other 1,2-bis(ferrocenyl)ethane derivatives. Crystal structures have also been determined for 2,2,6,6-tetramethyl-3-ferrocenyl-5-chloroheptan-3-ol, rac-1-hydroxy[3]ferrocenophane, rac-1S,3S-1,3-diphenyl-1-hydroxy[3]ferrocenophane, and of rac-1,1 ′-diphenyl-1,1 ′-(1,1 ′- ruthenocenediyl)dimethanol and show an intramolecular Cl⋯H–O hydrogen bond, a tetramer based on O⋯H–O hydrogen bonds, no hydrogen bonding, and a dimer with inter- and intramolecular O⋯H–O hydrogen bonds, respectively.