The electrochemistry of calixarene as a redox-dependent ionophore and its structural dependence are described. One or more redox-centers such as quinone, ferrocene, cobaltocenium and ruthenium bipyridine moieties have been introduced into the calixarene frame of the lower or upper rim. Although the electrochemical behavior depends mainly on the inherent redox property of these electrochemically active groups, the structural effect and solvent also play important roles, especially, in the presence of charged guests. When cationic species such as metal ions and ammonium ion are added to a quinone-functionalized calixarene solution, electron transfer to quinone is enhanced by the electrostatic effect or the formation of hydrogen bonds. In addition to redox-active hosts for voltammetric use, a number of calixarenes with novel structures have been developed as ionophores for potentiometric analysis and found to be successful for some target ions. In terms of Na+, Cs+ and Ca2+ selective ionophores for ion-selective electrodes, calixarenes are found to be excellent compared to crown ether derivatives or cryptands. Calixarenes can be also utilized to construct chemically modified electrodes, which are sensitive to gas species and biologically important compounds. The sophisticated design and synthesis of calixarenes are essential to specific potential applications to diverse fields.