The elucidation of the mechanism of potentiometric signals generation by liquid membrane electrodes incorporating undecylcalixresorcinarene derivatives upon stimulation by uncharged aniline derivatives is the main aim of the research presented. A series of molecules which play the role of host and guests in the molecular recognition process occurring at the aqueous-organic membrane interface were explored. It was proved that in the conditions where all aniline derivatives exist as uncharged molecules, cationic potentiometric signals were observed for all undecylcalixresorcinarene liquid membrane electrodes. The main parameters crucial for this phenomenon are the acidity/basicity of the hosts as well as the guests. The lipophilicity of the guests plays a secondary role.