Silver nanoparticles were electrodeposited from 0.3 M oxalic acid electrolyte on a pure aluminum working electrode under silver ion concentration-limited condition. A silver wire was held in a glass tube containing 1.0 M KCl solution as the counter electrode. Ion exchange between the glass tube and the main electrodeposition bath through a capillary was driven by the overpotentials as high as 10 V supplied by an electrochemical workstation. Due to the reaction between chlorine anion and silver cation to form AgCl solid at the Ag/AgCl electrode, the silver ion concentration-limited condition holds in the electrolyte. It is found that silver grows at the aluminum working electrode to form nanoparticles with an average size of about 52.4 ± 13.6 nm. With the increasing of the deposition time, the silver nanoparticles aggregate into clusters. The silver particle clusters are separated with approximately 112.6 ± 19.7 nm due to the hydrogen bubble-induced self-assembling, which is shown by the confined deposition of silver on a gold coating. The surface roughness of the aluminum substrate leads to the reduced uniformity of silver nanoparticle nucleation and growth.