An all-solid-state calcium-selective electrode was constructed with poly(pyrrole) solid-contact doped with calcium complexing ligand Tiron. The potentiometric response of this sensor can have a linear range down to 10(-)(9) M with a slope close to Nernstian and detection limit equal to 10(-)(9.6). The effects of pH and the activity of the interfering ion in the conditioning solution on the potentiometric behavior of the constructed sensors were examined. Potential stability, reproducibility, and impedance studies were performed. The selectivity of the constructed electrode is better than that of the conventional calcium-selective electrode with internal filling solution of 10(-)(2) M CaCl(2) and comparable to that of the best liquid-contact electrodes.