Monodisperse, quasi-spherical silver nanoparticles (Ag NPs) with controlled sizes have been produced directly in water via adding the aqueous solutions of the mixtures of AgNO3 and sodium citrate to boiling aqueous solutions of ascorbic acid (AA). Different compounds, including NaCl, NaBr, KI, Na2SO4, Na2CO3, Na2S, and Na3PO4, are added to the A(8)NO(3)/citrate mixture solutions to form new silver compounds with fairly low solubility in water, which are used as precursors instead of soluble Ag+ ions to synthesize Ag NPs via AA/citrate reduction. This enables us not only to produce monodisperse, quasi-spherical Ag NPs but also to tune the sizes of the resulting NPs from 16 to 30 nm according to the potential of new silver precursors as well as the concentrations of anions.