Metal or metallic nanoparticle dissolution influences particle stability, reactivity, potential fate, and transport. This work investigated the dissolution behavior of silver nanoparticles (Ag NPs) in three different shapes (nanocube, nanorod, and octahedron). The hydrophobicity and electrochemical activity at the local surfaces of Ag NPs were both examined using atomic force microscopy (AFM) coupled with scanning electrochemical microscopy (AFM-SECM). The surface electrochemical activity of Ag NPs more significantly affected the dissolution than the local surface hydrophobicity did. Octahedron Ag NPs with dominant surface exposed facets of {111} dissolved faster than the other two kinds of Ag NPs. Density functional theory (DFT) calculation revealed that the {100} facet elicited greater affinities toward H2O than the {111} facet. Thus, poly(vinylpyrrolidone) or PVP coating on the {100} facet is critical for stabilizing and prevent the {100} facet from dissolution. Finally, COMSOL simulations demonstrated consistent shape dependent dissolution as we observed experimentally.