The syntheses of two types of conformationally switched podand ionophores and their ionophoric properties are described. Both feature cyclohexane rings with polyether groups as trans 1,2 substituents. In the “switched off” forms of the ionophores, the two podand substituents are constrained to a diaxial orientation and cannot chelate a metal ion. In both cases, a chemical reaction, hydrolysis of a ketone acetal, is used to remove the constraint allowing the two podand substituents to achieve a diequatorial orientation. In this conformation, the two diequatorial podand substituents can chelate a potassium ion and the ionophoric properties are “switched on.” In one case, the chains can be held in the diaxial orientation by a large group, an acetyle group derivatized as the ethylene glycol acetal, in the 4 position. When the size of the group is lowered, the polyether groups become equatorial and can complex a potassium ion as evidenced by a conformational change measured by low temperature NMR spectroscopy. In the second example, an annulated ring holds the cyclohexane ring rigidly in the non-complexing conformation. When the restraint is removed, complexation can occur as evidenced by transport of potassium picrate through a liquid membrane (chloroform layer). In both cases, the ionophoric properties are “switched on” by hydrolysis of a ketone acetal. Chirality 10:78–87, 1998. © 1998 Wiley-Liss, Inc.