Silver particles with different degrees of aggregation were synthesized through a sodium dodecyl sulfate-assisted one-pot reaction in an aqueous medium. The products were characterized by transmission electron microscopy, scanning electron microscopy and UV-visible spectroscopy. The results showed that the degree of aggregation of the Ag nanoparticles could be tuned by changing the reaction parameters, such as the reaction temperature and time. A possible formation process of the Ag aggregate is proposed on the basis of a series of experimental results. Moreover, the surface-enhanced Raman scattering (SERS) effect of the Ag aggregates was evaluated by using rhodamine 6G as a Raman probe molecule. It was demonstrated that the SERS enhancement ability is related to the degree of aggregation of Ag particles, and a high SERS signal can be observed by selecting Ag nanoparticles with the proper degree of aggregation as substrates. Moreover, the aggregates showed good reproducibility and stability to SERS from organic molecules. Copyright © 2010 John Wiley & Sons, Ltd.