A simple and sensitive chemiluminescence assay for iodide (I(-)) detection was reported, which was based on iodide extracting Hg(2+) from DNA featuring a stem-loop structure containing T-Hg(2+)-T. Specifically, Hg(2+) induced random coiled G-rich single-strand DNA to form a stem-loop structure containing T-Hg(2+)-T. Because the binding of Hg(2+) and I(-) is much stronger than that of Hg(2+) and thymine (T), I(-) could extract Hg(2+) from the stem-loop structure, releasing the DNA, which then bound with K(+) and transformed into a K(+)-stabilized G-quadruplex (with hemin as a cofactor), which catalyzed the H(2)O(2)-mediated oxidation of luminol. The produced chemiluminescence as a sensing signal was applied to sensitively and selectively detect iodide with a detection limit of 12 nM. This system exhibited the first DNAzyme-based iodide sensor. Finally, the sensor was successfully applied for iodide detection in real lake water samples.