In the present study, we introduce the coordination of samarium-Q[5] systems in the absence and presence of the third species, and the corresponding supramolecular assemblies are dependent upon the addition of the third species. In the absence of the third species, a samarium cation (nitrate salt) coordinates to a Q[5] molecule and forms a molecular bowl; in the presence of an organic molecule (hydroquinone), a one-dimensional polymer of center dot center dot center dot Sm-Q[5]-Sm-Q[5]-Sm center dot center dot center dot is formed through direct coordination of Sm cation to the portal carbonyl oxygens. In the presence of nickel cations (chloride salt), an infinite ID supramolecular chain is constructed of samarium/cucurbit[S]uril molecular bowl through ion-dipole interaction and hydrogen binding; in addition, the stacking of the supramolecular chains forms a novel hexagonal open framework. Remarkably, in the presence of copper cations (chloride salt), Q[5]-based hexagonal netting sheets are constructed of 6-Q[5]-ring structures.