We demonstrate the pH-induced assembly of 2-mercaptosuccinic acid-functionalized silver nanoparticles (MSA-Ag NPs) in the absence of hard or soft template. Two-dimensional (2D) and three-dimensional (3D) networks of silver NPs were achieved by tuning pH of the medium. The assembly process was monitored using atomic forces microscopy. The key factor affects the formation of network of silver NPs may be intermolecular hydrogen bonding between two carboxylic acid groups of MSA on two adjacent silver NPs.