Abstract <p>The process of alkaline hydrolysis of the organophosphorus ecotoxicant paraoxon and carboxylic acid esters in micellar solutions of piperidinium carbamate-containing surfactants was studied using spectrophotometry. The influence of concentration and structural factors, as well as the holding time of surfactant solutions, on the catalytic effect of the systems was analyzed. During the hydrolytic decomposition of paraoxon, the highest catalytic activity was exhibited by the surfactant with a carbamate fragment at the quaternary nitrogen atom in the cycle (1-CB(Et)-P-16). The increase in the catalytic response for aged solutions of this surfactant was explained by its partial hydrolysis in a highly alkaline medium and the formation of a mixed system of 1-CB(Et)-P-16 with the product of its decomposition, 1-hexadecyl-1-(2-hydroxyethyl)piperidinium bromide. The formation of the latter was confirmed by ¹H NMR spectroscopy. In neutral solutions, the decomposition of piperidinium carbamate-containing surfactants did not occur for more than three to four months, indicating their hydrolytic stability under these conditions. In micellar catalysis of alkaline hydrolysis of carboxylic acid esters, a favorable effect of an increase in the hydrophobicity of the substrate (from <i>p</i>-nitrophenyl acetate to <i>p</i>-nitrophenyl caprate) and an alkyl substituent in the carbamate fragment of the amphiphile was established.</p>