Silver nanoparticles (AgNPs) are increasingly being incorporated into a range of consumer products and as such there is significant potential for the environmental release of either the AgNPs themselves or Ag+ ions. When AgNPs are exposed to environmental systems, the engineered surface coating can potentially be displaced or covered by naturally abundant macromolecules. These capping agents, either engineered or incidental, potentially block reactants from surface sites and can alter nanoparticle transformation rates. We studied how surface functionalization affects the dissolution of uniform arrays of AgNPs fabricated by nanosphere lithography (NSL). Bovine serum albumin (BSA) and two molecular weights of thiolated polyethylene glycol (PEG; 1000 and 5000 Da) were tested as model capping agents. Dissolution experiments were conducted in air-saturated phosphate buffer containing 550 mM NaCl. Tapping-mode atomic force microscopy (AFM) was used to measure changes in AgNP height over time. The measured dissolution rate for unfunctionalized AgNPs was 1.69 ± 0.23 nm/d, while the dissolution rates for BSA, PEG1000, and PEG5000 functionalized samples were 0.39 ± 0.05, 0.20 ± 0.10, and 0.14 ± 0.07 nm/d, respectively. PEG provides a steric barrier restricting mass transfer of reactants to sites on the AgNP surface and thus diminishes the dissolution rate. The effects of BSA, however, are more complicated with BSA initially enhancing dissolution, but providing protection against dissolution over extended time.