The interaction of a symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril (TMeQ[6]) with a series of lanthanide cations (Ln³⁺) was investigated in neutral water and in acidic solution. Analysis by single crystal X-ray diffraction revealed that different isomorphous families formed under different synthetic conditions. Such differences in the interaction between TMeQ[6] and Ln³⁺ could potentially be used for isolating heavier Ln³⁺ from their lighter counterparts in neutral solution, and lighter lanthanide cations from their heavier counterparts in acidic solution