A new optical sensor suitable for practical measurement of sodium in serum and whole blood samples is described. The optical sensor is based on a novel PET (photoinduced electron transfer) fluoroionophore immobilized in a hydrophilic polymer layer. The design concept of the fluoroionophore follows the receptor-spacer-fluorophore approach to sensor design using intramolecular PET-based signal transduction. Key to the development of this sensor is the identification of a nitrogen-containing, sodium-binding ionophore, coupled with a fluorophore having the correct spectral and electron-accepting properties. The slope of the sensor is approximately 0.5%/mM in the typical clinically significant range of 120-160 mM. This sensor has been implemented into a disposable cartridge, used for a commercially available critical care analyzer (Roche OPTI CCA) with precision better than +/- 1 mM (1 SD). The sensor displays excellent stability against hydrolysis and oxidation, leading to slope changes <5% after 9 months wet storage at 30 degrees C. On the basis of this design concept, fluoroionophores for other cations such as potassium, calcium and magnesium can be prepared by substitution of the ionophore.