We report a facile, selective, and sensitive colorimetric assay for Mn2+ ions based on the anti-aggregation of unmodified silver nanoparticles (AgNPs). In the absence of Mn2+ ions, the addition of l-arginine to the AgNPs dispersion caused the aggregation of AgNPs via Ag–N covalent interaction, and the color of the solution changed from yellow to colorless. While the presence of Mn2+ ions can prevent the aggregation of AgNPs due to the formation of the complex between Mn2+ ions and l-arginine, accompanying with a distinct color change from colorless to yellow with the increase of Mn2+ ions. Under the optimal experimental conditions, the absorbance at 390nm was linearly proportional to the Mn2+ ions concentration in the ranges from 0 to 700nM, and from 5μM to 70μM, with a detection limit of 20nM. Also, it was successfully used for the detection of Mn2+ ions in environmental water samples.