The interaction between the outer surface of cucurbit[6]uril (Q[6]) and methyl triphenyl phosphorus iodide (MTPI) has been studied in the presence of [CdCl4]2-. The MTPI is connected to four neighboring Q[6]s through weak interactions such as C-H···π and C-H···O, whilst the [CdCl4]2- is connected with the portal carbonyl oxygen, glycoside urea methylene and a bridging methylene of a Q[6] molecule via ion–dipole interactions. These interactions were evident from a single crystal X-ray diffraction study of Q[6]-MTPI-[CdCl4]2-. Furthermore, this complex exhibits a porous structure, which can be described as a Q[6]-based supramolecular framework (QSF), and its ability to adsorb iodine was also investigated.