The aggregation properties of supramolecular systems based on polyethyleneimines and cationic surfactants with a bicyclic head group - mono- and diquaternized derivatives of 1,4-diazabicyclo[2.2.2]octane are studied by surface tension measurements, potentiometry, conductivity measurement, and dynamic light scattering. The critical aggregation concentrations of individual and mixed systems based on them, as well as the size of the ensembles they form are determined. The relationship between the aggregation behavior and hydrophobicity of the polymer and the structure of the cationic surfactant is established.