Metal–organic frameworks (MOFs) can provide a variety of nanocompartments for the confinement of guest molecules. Furthermore, the emissions of fluorescent molecules can be tuned by confinement. In this study, a solvent-free “bottle-around-ship” method is used to encapsulate perylene and 9,10-dimethylanthracene, two polycyclic aromatic hydrocarbons, in the MOF ZIF-8. Luminescence color tuning is achieved, including white-light emission, when controlling the loading of only a single type of guest. Photophysical analysis suggests that the variations in luminescence result from various guest arrangements in the nanocompartments, as well as host–guest interactions. Because of the tight confinement of the guests, this host–guest system displays excellent luminescence thermal stability.