Cocrystals composed of a pyrogallol[4]arene molecule (one of C-propylpyrogallol[4]arene in ethanol and one of C-hexylpyrogallol[4]arene in isopropanol) and a pyrene molecule were crystallized and investigated with the aim to develop trends based on solvent and aliphatic tail length of the pyrogallol[4]arene. These new trends along with previously determined trends for the fluorescent probe 1-(2-pyridylazo)-2-naphthol (PAN), were then used to crystallize a cocrystal composed of C-hexylpyrogallol[4]arene and two fluorescent probes, pyrene and PAN. Within a two-component cocrystal of pyrene or PAN, the probe molecules are complexed in both the endo (inside the pyrogallol[4]arene bowl) and exo (outside the pyrogallol[4]arene bowl) positions. However, in the three component system, selective complexation of the probes is demonstrated whereby the PAN molecules prefer to be endo and the pyrene molecules occupy exo positions.