Previously, we reported a guest molecule containing a viologen (V), a phenylene (P) and an imidazole (I) fragment (VPI) forming a host : guest 2 : 2 complex with cucurbit[8]uril (CB[8]) and an unprecedented 2 : 3 complex with cucurbit[10]uril (CB[10]). To better address the structural features required to form these complexes, two VPI analogues were designed and synthesized: the first with a tolyl (T) group grafted on the V part (T-VPI) and the second with a naphthalene (N) fused on the imidazole (I) part (VPI-N). While VPI-N afforded a discrete well-defined 2 : 2 complex with CB[8] and a 2 : 3 complex with CB[10], T-VPI organized also as a 2 : 2 complex with CB[8] but no well-defined complex was obtained with CB[10]. These complexes were studied by NMR spectroscopy, notably DOSY, which allowed us to estimate binding constants for 2 : 2 complex formation with CB[8], pointing to more stable 2 : 2 complexes with more hydrophobic guests. UV-vis and fluorescence spectroscopy confirmed complex formation, suggesting host-stabilized charge-transfer interactions. Therefore, the simple addition of CB[8] or CB[10] enabled us to control the level of guest stacking (dimer or trimer) using relevant pairs of synthetic hosts through spontaneous host : guest quaternary or quinary self-assembly.