The electrochemistry and electronic absorption spectroscopy of samarium, europium, and ytterbium were investigated in the 1-(1-buty1)trimethylammonium bis(trifluoromethylsulfonyl)imide (BuMe3NTf2N) and 1-buty1-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BuMePyroTf(2)N) ionic liquids and in these solvents containing the neutral tridentate ligand N,N,N ',N '-tetraocty1-3-oxo-pentane diamide (TODGA) and the anionic hard ligand chloride. Lanthanide ions were introduced into the ionic liquids by controlled potential oxidation of the respective metals to yield solutions containing Eu2+, Sm3+, and Yb3+, and it was possible to cycle between Eu2+ and Eu3+ as well as Yb3+ and Yb2+ using controlled potential electrolysis. Electronic absorption spectroscopy suggested that the Ln(3+) species are wealdy solvated by Tf2N anions as [Ln(Tf2N)(x)]((x-3)-) in the neat ILs. The quasireversible Ln(3+/2+) couples of all three elements were readily accessible in these ILs, but Sm2+ was only stable on the voltammetric time scale. Addition of TODGA to [Ln(Tf2N)(x)]((x-3)) solutions produces 3:1 complexes with Eu3+ and Sm3+ but only a 2:1 complex with the smaller Yb3+ ion. Depending on the temperature, addition of Cl to solutions of [Ln(Tf2N)(x)]((x-3)-) induces precipitation of LnCl(3)(s) when the mole ratio mCl(-) /mLn(3+) approximate to 3. However, when mCl(-)/mLn(3+) > 3, these precipitates redissolve to form the octahedral chloride complexes, [LnCl(6)](3-).