Phosphorylation of alkylated polyethyleneimine in chloroform in the presence of alkylated calyx[4]-resorcinolarenes with 2-hydroxyethoxy- and phosphorus-containing substituents and cetyl(3-hydroxypropyl)-dimethylammonium bromide was studied by means of the UV spectrophotometry. It was found that the character and the degree of the effect of calyxarene and its mixture with the surfactant depend on the hydrophobicity of macroring and the ratio of concentrations of components in the solution. The increase in the content of calyxarene and decrease in the concentration of polymer leads to the transformation of the catalytic action into the inhibiting one.