Supramolecular chemistry is a multidisciplinary research area mostly associated with the investigation of host-guest interactions within intricate three-dimensional (3D) molecular architectures held together reversibly by various non-covalent interactions. Continuous efforts to develop such kinds of complex host-guest systems with designer oligopyrrolic macrocyclic receptors are a rapidly growing research domain, which is deeply involved in applied supramolecular chemistry research. These host-guest supramolecular complexes can be constructed by combining suitable electron-rich oligopyrrolic donors (as a host) with complementary electron-poor guests (as acceptors), held together by the ionic force of attraction triggered by intermolecular charge/electron transfer (CT/ET) transitions. Some of these resulting CT/ET ensembles are potential candidates for the construction of efficient optoelectronic materials, optical sensors, molecular switches, etc. In this Feature Article we aim to focus on these supramolecular ensembles composed by size and shape complementary electroactive oligopyrrolic molecular containers, which are suitable for spherical guest (e.g., buckminsterfullerene) complexation. We also provide a "state-of-the-art" overview on plausible applications of these particular host-guest systems. Our aim is to cover only specific electron-rich tetrathiafulvalene (TTF)-based oligopyrrolic receptors, e.g., TTF-calix[4]pyrroles, TTF-cryptands, TTF-porphyrins and exTTF-porphyrin-based molecular motifs reported to date, along with a brief outlining of their "functional behaviour" in materials chemistry research.