The behavior of linear and cyclic fluorinated 1,3,5-triketones and their metal derivatives towards common halogenating agents was examined, and optimal reaction conditions for the straightforward synthesis of mono-, di-, and tetrahalogenated products were found (Schemes 1-3). An aromatization through a double HBr elimination from an ,-dibrominated cyclohexanone was shown to be a promising synthetic route to 1,1-(2-hydroxy-1,3-phenylene)bis[2,2,2-trifluoroethanones] (= 2,6-bis(trifluoroacetyl)phenols; Scheme 4). Additionally, the 1,3,5-triketones prepared add readily H2O or alcohols to produce novel bridged 2,6-dihydroxypyran-4-ones (Scheme 2). The structure of the obtained compounds 6a and 7a was confirmed by X-ray structure analysis.