A new PVC membrane electrode for the triiodide ion based on a charge- transfer complex of iodine with 7,16-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane as a membrane carrier was prepared. The electrode exhibits a Nernstian response for triiodide ions over a wide concentration range (1.0 ×10-1- 1.0 ×10-5) with a slope 59.3 ± 0.9 mV decade-1 and a detection limit of 6.3 ×10-6 M. It has a response time of 3o s and can be used for at least 3 months without any divergence in the potential. The potentiometric response is independent of the pH, in the pH range 1.6-10.0. the proposed electrode has shown very high selectivity for the triiodide ion over a wide variety of other anions. This electrode was successfully applied as an indicator electrode in the potentiometric titration of ascorbic acid and hydroquinone from pharmaceutical preparations as well as ascorbic acid in orange juice and dissolved O2 in tap water