Abstract A fast and efficient supported liquid membrane (SLM) extraction system for the series of substituted aromatic aminophosphonates was elaborated. The mass transfer of solute was examined in terms of operator (pH and ionic strength of water phase, composition of membrane phase and the concentration of analyte) dependent parameters. Additionally, the influence of the aminophosphonates structure on the extraction efficiency was examined. From the results it can be concluded that the most effective conditions of membrane process are 10% (w/w) carrier concentration (Aliquat 336) in the liquid membrane, high pH of donor phase (pH=11) and moderate salt concentration (0.4 M NaCl) in the acceptor phase to create sufficient driving force of the process. The results concerning the influence of the aminophosphonates structure show that the overall mass transfer is dependent on the interchanging factors such as acidity, hydrophobicity and properties of the analyte–carrier complex.