Reactions of bis(pentafluorophenyl)mercury with piperidine, sodium iso-propoxide or sodium tert-butoxide have yielded the corresponding 4-substituted tetrafluorophenylmercurials, [Hg(C6F4X-4)2] (X = cyclo-C5H10N (1), OCH(CH3)2 (2), OC(CH3)3 (3)), in reasonable yields but the bulkier nucleophiles, cis-2,6-dimethylpiperidine and 2,6-di-iso-propylphenolate (from sodium 2,6-di-iso-propylphenolate) decomposed the mercurial into pentafluorobenzene. Treatment of bis(pentafluorophenyl)mercury with another bulky nucleophile, 2,6-diphenylphenolate (from sodium 2,6-diphenylphenolate), in methanol, resulted in the unexpected formation of [Hg(C6F4(OMe)-4)2] (4). The structures of all the mercurials have linear C–Hg–C stereochemistry with two coplanar aryl rings. Amongst a complex series of supramolecular interactions, Hg⋯O bonding is observed for the alkoxy substituted mercurials but there are no Hg⋯N interactions in the structure of bis(2,3,5,6-tetrafluoro-4-piperidinophenyl)mercury.