This paper describes a facile method that generates dimers of Ag nanospheres by etching Ag nanocubes with Fe(NO 3 ) 3 in ethanol with the assistance of poly(vinyl pyrrolidone) (PVP). During the etching process, the corners and edges of the Ag nanocubes were truncated off to generate spherical particles, accompanied by dimerization as a result of reduction in colloidal stability due to the addition of ionic species. Both ethanol and PVP play an important role in the etching and dimerization processes. By starting with Ag nanocubes of different sizes, we obtained welldefined dimers of Ag spheres 40, 63, and 80 nm in diameter with percentages of dimerization >60%. Since this approach can be used to fabricate dimers of Ag nanospheres with a range of different sizes, it allows for a systematic study of the hot-spot phenomenon in SERS. By correlating with SEM imaging, we measured the SERS enhancement factors for individual dimers from the three different samples, and an average value of 3.9×10 7 , 9.3×10 7 , and 1.7×10 8 was obtained, respectively.