Owing to their unusual Lewis acidic properties, the coordination chemistry of fluorinated organomercurials is attracting increasing interest. In this review, the authors focus on the synthesis, structures, and properties of neutral Lewis adducts involving fluorinated organomercurials such as (CF 3 ) 2 Hg, (C 6 F 5 )HgCl, (C 6 F 5 ) 2 Hg, and [(o-C 6 F 4 )Hg] 3 . While most of these organomercurials form adducts with common Lewis basic organic substrates, [(o-C 6 F 4 )Hg] 3 also interacts with aromatic hydrocarbons, alkynes, N-heterocycles, and metallocenes to form π-complexes. In some cases, this complexation mode results in the formation of supramolecules with unusual luminescence properties or microporosity.