The reactions of BiCl 3 with 2,4,6-tris(trifluoromethyl)phenyl lithium (LiR f) in ether solution in 1 : 2 and 1 : 3 ratios have led to the isolation of Bi(R f) 2Cl ( I) and Bi(R f) 3 ( II). The hexane-soluble compounds have been spectroscopically and structurally characterized I: monoclinic space group P2 1/ c, a = 8.816(2), b = 30.459(6), c = 8.817(2)Å, β = 109.58(2)°, Z = 4, V = 2230.7(8)Å 3; II: monoclinic space group P2 1/ c, a = 11.769(2), b = 17.029(3), c = 16.213(3)Å, β = 102.74(3)°, Z = 4, V = 3169.3(10)Å 3. Both compounds are monomeric in the solid state. Compound II is unstable in solution even under inert atmosphere producing R fH. In the solid state the compound is stable in inert atmosphere but decomposes slowly upon exposure to air producing R fOH and (R f) 2O. In the presence of BiCl 3, II undergoes exchange to produce I and another complex which is probably Bi(R f)Cl 2.