Metal nanoparticles (NP) are very attractive because of their size- and shape-dependent properties. A widely used preparation of ligand-stabilized metal NP is the two-phase liquid-liquid method using dodecanethiol (DT) as ligand. This work presents various procedures to synthesize dodecanethiol-capped silver NPs, all of them based on a two-phase liquid-liquid method. Small alterations in the synthetic parameters lead to dramatic modifications in the nanoparticles' average size, size distribution width, stability, and structure, as well as in their ability to self-assemble. (c) 2005 Elsevier Inc. All rights reserved.