Three ligands bearing triphenylamine as a core and one, two or three acyclic polyamine chains, TPA1p, TPA2p and TPA3p, respectively, have been studied by potentiometric and photophysical (UV-Vis, steady-state and time-resolved fluorescence) techniques. The host-guest interaction with cucurbit[7]uril, CB7, has been investigated in aqueous solution showing aggregation induced emission behaviour when encapsulated into a CB7 cavity. From fluorescence emission it is revealed that the charged polyamine chains are the unit entering into CB7 and from the Job plots the stoichiometries are found to vary from 1 : 1 to 1 : 3 L : CB7 ratios. Interactions of the charged amines with the portals of CB7 restrict rotation of the benzene units in the triphenylamine backbone (free rotor effect), decreasing the radiationless internal conversion channel at the expense of the enhancement of fluorescence. Dynamic light scattering and resonance Rayleigh scattering experiments show that TPA3p-CB7 complexes involve formation of aggregates with a mean size of 126 ± 5 nm and a dispersity factor of 0.117, indicating a monodisperse distribution and supporting the important conclusions of this work: formation of emissive aggregates through the AIE effect.