A synthetically directed self-assembly strategy to the aqueousphase synthesis of twinned crystalline silver/silver homojunction nanopartides (Ag/Ag HJNPs) is demonstrated. In the self-assembly, ethylenediamine tetraacetic acid disodium (EDTA) and solution pH values play a crucial role in the formation of Ag/Ag HJNPs while the sizes of Ag nanoparticles (NPs) in the Ag/Ag HJNPs depend on the reductant concentrations of ascorbic acid. surface enhanced Raman scattering (SERS) measurements indicate that the SERS intensity acquired from the Ag/Ag HJNP colloidal solution is about 200 times stronger than that obtained from isolated Ag NP, colloid solution. The plasmonic and SERS behaviors of Ag/Ag HJNPs were simulated by discretedipole approximation (DDA) and three-dimensional finite difference time domain;(3D-FDTD) methods, respectively. Theoretical calculation results disclose;,that;:Surface:, plasmon resonance (SPR) properties of the Ag/Ag:4 HJNPS are different from those of isolated Ag nanospheres, and their maximal SERS enhancement is about 2 orders of magnitude higher than that of isolated Ag nanospheres, which is in good agreement with the experimental results. The extra SERS enhancement can be explained by the hot spots at homojunction structures between Ag particles because of near-field coupling effect.