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Rapid and sensitive detection of heavy-metal ions in natural water environments worldwide is urgently needed because of their severe threats to human health. In the present work, monolayer graphite-like flake C3N4 (g-C3N4) materials were applied as a new fluorescent sensor for the detection of trace silver ion in aqueous solution. The thickness of synthesized g-C3N4 was 0.45 nm and obtained by exfoliating twice with ultrasonic. With the presence of ethylene diamine tetraacetic acid as a screening agent, the highly sensitive sensor reached a low detection limit of 52.3 nmol/L for silver (I) ion and there was no disturbance when silver (I) ion coexisted with other metal ions in water samples. Under the optimal conditions, the monolayer g-C3N4 was successfully used to detect trace silver (I) ion in different environmental water and drinking water samples.