The polymer-colloid complexes that form in solutions of polymers and nonmacromolecular amphiphilic compounds as a result of noncovalent interactions can function as nanoreactors produc ing metal nanoparticles [1] and catalysts for the hydrolysis of phosphorus acid esters [2, 3] and 2 (4 alkoxyphenyl) 1,3 dioxolanes [4]. The amphiphilic component can be a conventional surfactant (anionic, cationic, or nonionic) [5], a pyrimidi nophane [6,7], or a calixarene [8,9]. In the latter case, in addition to the sorption and solubilization binding of the reactants by the polymer-colloid aggregates, there can be inclusion type interactions [5] that enhance the reactant concentrating effect and are thus favorable for the catalytic action of the system.Here, we report the catalytic activity of supramo lecular systems based on alkylated polyethyleneimine, cationic surfactants with different structures, and calix[4]resorcinarenes (CRs) with 2 hydroxyethoxy and phosphorus containing substituents on the upper rim and alkyl substituents on the lower rim of the mac romolecule in chloroform.The polymer component was branched polyethylene imine modified with alkyl (n tetradecyl) substituents (APEI). The molar mass of its unit was 229. The degree of substitution (ratio of the number of substi tuted polyethyleneimine fragments to the number of unsubstitued fragments) was 0.6. The surfactants had a cyclic or bicyclic head. The former group of surfac tants consisted of hexadecylpyridinium bromide (HPB) and N octadecyl N (2 hydroxyethyl)piperi dinium bromide (OHPB), and the latter consisted of alkylated derivatives of 1,4 diazabicyclo[2.2.2]octane (AD 12, AD 16, and AD 18):Abstract-The kinetics of phosphorylation of alkylated polyethyleneimine in chloroform in the presence of cationic surfactants with a cyclic or bicyclic head group and alkylated calix[4]resorcinarenes has been inves tigated by UV spectrophotometry. The catalytic activity of individual and mixed solutions of the amphiphilic admixtures depends on the structure of the constituents of the composition, on their concentrations in the solution, and on their relative amounts. In the presence of a calixarene, a decrease in the surfactant and poly mer concentrations enhances the catalytic effect of the system.