A one-pot synthesis of 2-perfluoroalkanoylcyclohexane-1, 3-diones via C-acylation of cyclohexane-1, 3-diones with N-perfluoroacylimidazole as an acylating agent is reported. A reaction was examined with isolated N-trifluoroacetylimidazole and with N- perfluoroacylimidazoles generated in situ from perfluorocarboxylic acid anhydrides or perfluorocarboxylic acids.