Vitamin C is an essential biological molecule for living organisms. The detection of vitamin C is always required due to its wide use in chemical, biological and pharmaceutical engineering. Here, we established a novel sensing system for rapid, ultrasensitive and highly selective detection of vitamin C based on a 'turn-on' fluorescent method. The turn-on fluorescent sensing system was built up of a colloidal CePO(4):Tb nanocrystalline solution with its fluorescence quenched by KMnO(4). The addition of vitamin C leads to a linear increase of fluorescence. The sensing principle of nanocrystalline CePO(4):Tb is based on a redox reaction via simply modulating the surface chemistry of nanocrystals. Our present sensing system for vitamin C exhibits a rapid response rate of less than 2 min, and highly selective and ultrasensitive detection with a detection limit of 108 nM, which is two orders of magnitude lower than that acquired by previously reported methods. The repeated reversibility of fluorescence quenching/recovery with time revealed a high reproducibility and long-term stability of our sensing materials. Furthermore, our developed sensing material overcomes the disadvantages such as complex surface modification/immobilization and serious biotoxicity compared to quantum-dot-based fluorescent sensing systems.