The mechanism of the generation of potentiometric signals of corrole- and calix[4]pyrrole-containing liquid membrane electrodes was elucidated and compared in the presence of the neutral forms of phenol derivatives. In addition, the influence of lipophilic, anionic or cationic salts on this phenomenon was explored. Finally, the relationship between the acid-base properties of the phenolic guests and the hydrogen bond donor activity of the calix[4]pyrrole and corrole hosts, and the influence on the molecular recognition phenomenon occurring at the organic/aqueous interface are discussed.