On the basis of a seven-step synthetic route, the total synthesis of 7-azamelatonin, an analogue of melatonin, has been achieved with an overall yield of approximately 9.2%. In aqueous solution, 7-azamelatonin exhibits a unique excited-state double proton transfer (ESDPT) property, resulting in dual emission bands (405 and 560 nm). The ESDPT property makes 7-azamelatonin superb as a potential molecular probe for future bioapplication and for pharmacological research.