New potentiometric sensors with polymeric plasticized membranes based on ionic associates of sodium dodecylsulfate (DDS) and cationic complexes of copper(II) with some organic reagents (1,10‐phenanthroline (Phen), N,N′‐bis(salicylidene)ethylenediamine (Salen), α,α′‐dipyridyl (Dipyr) were developed for quantitative determination of homologous sodium alkylsulfates in a wide concentration range 2.0×10−7 (5.0×10−7)–1.0×10−2 (5.0×10−4) M. The low detection limit of DDS was 1.0×10−7 M (28.8 μg/L). The electrodes demonstrated good and extremely stable response to sodium alkylsulfates and were successfully applied to determination of anionic surfactants in water solutions, technical raw preparations, detergents, cosmetic and cleaners.