New lipophilic triesters of calix[4]arene and calix[4]quinone are investigated as sodium ion-selective ionophores in poly(vinyl chloride) membrane electrodes. For an ion selective electrode based on calix[4]arene triester I, the linear response is 1 ${ imes}$10-3.5 to 1 ${ imes}$ 10-1 M of Na+ concentrations. The selectivity coefficients for sodium ion over alkali metal and ammonium ions are determined. The detection limit (logaNa+ = -4.50) and the selectivity coefficient (logKNa+,K+pot = -1.86) are obtained for polymeric membrane electrode containing calix[4]arene triester I.