Host−guest complexation of small heterocyclic (guest) and macrocyclic cavitands (hosts) organic molecules is still to date a very popular, inexpensive approach that bypasses the burdens of conventional covalent synthesis. Understanding the selection criteria of these chemicals is crucial to the design and potential applications of their supramolecular assemblies. This review surveys examples within the last fifteen years (2005-2020) of supramolecular complexes in which the interacting photoinduced electron transfer (PET)-based chromophore and quencher fragments are commonly used in the market with reported CAS numbers. It appears from this survey that the supramolecular effects can be directed to specifically disrupt PET when the non-emissive macrocycles separately encapsulate the fluorescent acceptor or donor molecules, among other specific factors, such as when inducing conformational changes or pKa shift of the donor. On the contrarily, synergetic encapsulation of both donor and acceptor molecules, formation of ternary self-assembly at the rim, or encapsulation of one component while grafting the other onto the macrocycle, among other specific factors such as the modulation of the excited-state structure of donor will lead to the enhancement of PET process. In the event the donor or acceptor molecules have multitopic structures, the PET process can repeatedly be switched on and off. It is generally concluded that understanding the criteria for the combination of these available products for the purpose of manipulating their PET efficiency should pave the way for the facile alternative generation of new non-covalently bonded host−guest supramolecular assemblies with a more specific design tailored for more advanced, diverse, and economic applications such as chemical sensing, molecular gates, drug delivery, and biolabeling.