Coordination and supramolecular assemblies of a fully substituted cyclopentanocucurbit[6]uril (CyP6 Q[6]) with a series of lanthanide cations (Ln(3+)) have been investigated in the presence of tetrachlorozincate anion ([ZnCl4](2-)). X-ray single-crystal diffraction analysis has revealed that the interaction of CyP(6)Q[6] and a series of Ln(3+) cations unexpectedly results in the formation of at least seven different CyP(6)Q[6]-based coordination complex adduct and supramolecular assemblies groups, including with (1) La3+, Ce3+ cations; (2) Pr3+, Nd3+ cations; (3) Eu3+, Gd3+, Tb3+, Dy3+ with P (1) over bar or P1 space group, in which CyP(6)Q[6] molecules coordinate alternatively with Ln(3+) cations and form linear coordination polymers; (4) CyP(6)Q[6] molecules interact alternatively with [Ho(H2O)(8)](3+) aqueous complexes and form linear supramolecular chains; CyP(6)Q[6] molecules can assemble two different Ln(3+) free porous supramolecular assemblies from CyP(6)Q[6]-Ln(NO3)(3)-ZnCl2-HCl systems, Ln = Tm, Yb, and Lu; however, no solid crystals were obtained from system containing Er3+ cation. Thus, these differences could lead CyP(6)Q[6] to be useful in not only the isolation of lighter lanthanides from their heavier lanthanides but also special selectivity for different volatile organic compounds.