An electrochemical procedure, based on the dissolution of a metallic anode in an aprotic solvent, has been used to obtain silver nanoparticles ranging from 2 to 7 nm. By changing the current density, it is possible to obtain different silver particle sizes. The influence of the different electrochemical parameters on the final size was studied by using different kinds of counter electrodes. The effect of oxygen presence in the reaction medium as well as the type of particle stabilizer employed have also been investigated. In some conditions an oscillatory behavior is observed. Characterization of particles was carried out by TEM and UV−vis spectroscopy. The maximum and the bandwidth of the plasmon band are both strongly dependent on the size and interactions with the surrounding medium. The presence of different silver clusters was detected by UV−vis spectroscopy. By using this technique, the existence of an autocatalytic step in the synthesis mechanism is proposed.