This Feature Article provides an account of the recent work by our research group (with some reference to relevant work of other groups) on the spectacular physico-chemical properties of cucurbituril-based supramolecular assemblies of chromophoric dyes having technological and biological importance. Simultaneous association of multiple hosts or guests either by cooperative binding or competitive displacement is an applied strategy to construct novel functional assemblies with predesignated characteristics. Here, effort has been made to briefly discuss the diverse photophysical characteristics of several host–guest complexes and the dynamic responses of such molecular assemblies towards external stimulants like metal ions. The detailed experimentation on these assemblies project their applications in the controlled uptake and release of drugs, photofunctional devices, aqueous-based dye lasers, and molecular architectures.