For mono-and dicationic surfactants with trimethylammonium (TMA), triphenylphosphonium (TPP), and 4-aza-1-alkyl-1-azoniabicyclo[2.2.2]octane (DABCO) polar groups, and also for pyrimidinic amphiphiles, a correlation is revealed between their aggregation and solubilization properties and their complexation capacity toward an oligonucleotide. Mixed cationic surfactantcalixarene systems demonstrate controllable binding/ release properties.Cationic surfactants are very attractive for the design of catalytic systems, analytical separation, antimicrobial compositions, and synthetic vectors for gene delivery.1,2 In these strategies, the capacity of surfactants to adsorb on surfaces or to bind guest molecules is utilized. Nanocontainers based on surfactants are noncovalently bound dynamic structures, and they should therefore be competitive with carriers based on covalently formed polymer containers and polyelectrolyte capsules fabricated by the layer-by-layer technique. The advantages of surfactant-based nanocontainers are their easy preparation, versatile uses, controlled morphology and size, low required concentration, and biocompatibility. Therefore, to be competitive from the viewpoint of current technologies, cationic surfactants have to meet the above criteria and exhibit high micellization and solubilization capacities and low toxicity. The morphology of aggregates, their binding capacity, and hence, their functional activity depend to a great extent on the chemical structure of amphiphiles. Herein, micellar systems based on cationic surfactants are studied with variation of the nature of the charge atoms. In particular, mono-and dicationic surfactants with trimethylammonium (TMA-n), triphenylphosphonium (TPP-n), and 4-aza-1-alkyl-1-azoniabicyclo[2.2.2]octane (DABCO-n) polar groups, as well as pyrimidinic mono-and dicationic amphiphiles, are considered, with the number of carbon atoms in the alkyl chain n varied from 8 to 18. The data obtained are exemplified by the hexadecyl derivatives TMA-16, Generally, different methods are used to estimate the aggregation behavior, in particular, tensiometry, conductometry, NMR self-diffusion, dye solubilization studies, and so on. The data obtained are analyzed in terms of the concentration dependences of the measured parameters, and breakpoints in the plots are identified as critical micelle concentrations (cmc's). These values indicate the onset of micellization in the systems. In our earlier works, 36 the micellization of cationic surfactants with different headgroups was studied through a combination of methods. Surfactants with charged nitrogen (TMA and DABCO series) showed very similar cmc's of around 1 mM, while phosphonium salts demonstrated much lower cmc values.3,5 The advantages in terms of micellization capacity may result in more effective functional activity. Therefore, the purpose of this study is to compare their binding capacity toward different guests, including hydrophobic organic substrates and an oligonucleotide.As seen in Figure 1, a higher solubiliza...