This work presented an easy synthesis method for water‐soluble, green and fluorescent silver nanoclusters with poly (methacrylic acid) (AgNCs@PMAA) and preliminarily explored their ability to detect Fe2+ by measuring their fluorescence quenching. The acquired AgNCs@PMAA showed steady, selective, and highly sensitive detection of Fe2+. The Fe2+ detection limit for AgNCs@PMAA was 3 μM, and a linear relationship was observed at 5–150 μΜ ion concentration. AgNCs@PMAA had no biological toxicity and could be used for in vivo imaging and detection of iron ions. This fluorescence detection method based on novel nanomaterials exhibits future application in biolabeling, biosensing, and other purposes.