A majority of optically functional materials can be perceived as a liaison between ionic or molecular guests and a more or less rigid host. The guests exhibit an optical function, whereas the host provides suitable space, both of them synergistically complementing each other. The embracement of guests and hosts is often very intimate, as e.g. in typical phosphors, where luminescent ions even become part of the host. While the host–guest terminology usually is not applied to such marriages, the term becomes appropriate, if the host grants some degrees of spatial freedom, yet giving order and structure to its guests. Zeolites, clays and inverse opals are porous materials naturally providing hospitable cavities, channels or other compartments, and at the same time the guests are often demanded to occupy preassigned positions within these, or to structurally adapt to the interior host topology. Whereas zeolites and clays are merely patient providers of guest space, inverse opals, can actively turn the light on and off. The present article summarises and highlights recent experimental evidence, ongoing research and some envisaged merits resulting from the interaction of matrix confined luminescent ions, complexes and molecules with a focus on the optical properties of rare earth based materials.