The interaction of a series of lanthanide cations (Ln³⁺) with inverted cucurbit[7]uril (iQ[7]) in the presence of [ZnCl₄]²⁻ anions as a structure-directing agent have been investigated. Single-crystal X-ray diffraction analysis has revealed that the [ZnCl₄]²⁻ anions surround the iQ[7] molecules via the outer surface interactions of iQ[7]. This results in the formation of honeycomb-like frameworks, and ultimately linear supramolecular chains of iQ[7] in which Ln³⁺ cations occupy voids within the framework. Moreover, these iQ[7]/Ln³⁺-based supramolecular assemblies exhibit excellent thermal stability as well as permanent porosity, and in one case screening revealed a high CH₃OH uptake capacity compared with other porous organic materials assembled solely through hydrogen bonding under ambient conditions.