The formation of host/guest complexes between cucurbit[7]uril (CB7) and tetradecyltrialkylammonium bromide surfactants with trimethyl (C TMA ), triethyl (C TEA ), and tripropyl (C TPA ) head groups was studied. Complexation was studied by ESI-MS, isothermal titration calorimetry (ITC), and NMR spectroscopy. The structure of the complexes is strongly dependent on the surfactant head group. Both 1:1 and 2:1 complexes are formed with all cationic surfactants. The magnitude of the K binding constants decreases with the alkyl length of the head group, whereas that of the K binding constants is independent of the nature of the surfactant head group. Distinct structures were found for the 1:1 and 2:1 complexes. C TMA and C TPA surfactants form 1:1 inclusion complexes that comprise the head group close to the CB7 portal and 2:1 external complexes with both host molecules near the head group. The 1:1 complexes between C TEA and CB7 showed that the head group was centered inside the CB7 cavity, whereas in the 2:1 complex the second molecule of CB7 was located at the end of the main alkyl chain.