The local deposition of Ag nanoparticles (NPs) on omega-mercaptoalkanoic acid, HS(CH2)(n)CO2H, (n = 2, 10) self-assembled monolayers (SAMs) by scanning electrochemical microscopy (SECM) is reported. We found that the presence of a SAM had a pronounced effect on Ag deposition. Experiments were conducted by applying different potentials to an Au(1 1 1) substrate either in the presence of a constant concentration of Ag+ ions in solution (bulk deposition) or by generating a flux of Ag+. from an Ag microelectrode that was positioned close to the Au(1 1 1) substrate (SECM deposition). SECM was used for generating a controlled flux of silver ions by anodic dissolution of an Ag microelectrode close to the SAMs modified Au(1 1 1). We found that the shape of the NPs was affected by the length of the carbon-chain of the SAM. Tetrahedral NPs were obtained on bare Au(1 1 1) surfaces while rod like and cubic Ag NPs were deposited onto 3-mercaptopropanoic acid (MPA) and 11-mercaptoundecanoic acid (MUA) SAMs, respectively. The size and shape of the deposited NPs were influenced by the deposition potential. We conclude that the shape and distribution of locally deposited Ag NPs on Au(1 1 1) can be controlled by modification of the substrate with a SAM and through controlling the Ag+ flux generated by SECM. (C) 2011 Elsevier Ltd. All rights reserved.