Nanometer-sized silver particles were synthesized by using didecylamine dithiocarbamates as the protecting ligands. With control of the initial ligand-metal feed ratios, the core diameter of the resulting particles was found to vary from about 5 to 2.5 nm, as determined by transmission electron microscopic measurements. The core size dispersity was also found to decrease with increasing feed ratio. In UV-visible spectroscopic studies, the particle surface plasmon resonance peak diminished in intensity as the particle core size decreased, whereas in electrochemical measurements, smaller sized particles gave rise to well-defined quantized charging voltammetric features, in contrast to the featureless responses with the larger particles. Such single electron-transfer behaviors were consistent with those observed in STM measurements involving individual nanoparticles. Overall, this study provides an effective approach to the synthesis of stable nanometer-sized silver nanoparticles with interesting electronic and electrochemical properties.