The synthesis of [RhF(COD)](n) and its triphenylphosphine adduct 2, and a preliminary study of the reactivity of 2 are reported. The reactivity of the Rh-F bond is illustrated by the reactions that lead to compounds 5 and 6. Compound 5 is the first trifluoromethyl Rh(I) complex characterized by monocrystal X-ray diffraction. Both compounds 2 and 6 are initiators of the polymerization of phenylacetylene.[GRAPHICS]