By means of the dielcometric titration and the dynamic light scattering, the association in the systems based on the alkylated polyethylenimines, hydroxyalkyl cationic surfactants, and calix[4]arenes in chloroform was studied. By means of the UV spectrophotometry the catalytic effect of the aggregates formed on the phosphorylation of polyethylenimines was established. Catalytic effect of the system depends on the structure of surfactants and calixarenes, and also on the relative content of the solution components.