The possibility of transporting several transition metal picrates (Cu2+, Ni2+, Co2+, and Fe3+) through an active transport membrane with a pH gradient was investigated. Two new macrocyclic ligands used as carriers, 5,11,17,23,29,35-hexa-t-butyl-37,38,39,40,41,42-hexakis-[n-(1-epoxyethyl)methoxy]calix[6]arene (I-6-EPO) and 5,11,17,23,29,35-hexa-t-butyl-37,38,39,40,41,42-hexakis-[n-(2-hydroxyaminoethyl)methoxy]calix[6]arene (I-6-HPA), were synthesized from p-tert-butylcalix[6]arene. It was found that the membrane system studied allows separation of some transition metal cations.