Surface-enhanced Raman scattering (SERS) is a powerful technique that has been widely applied in different fields to identify molecular structures and characterize atomic interactions. In this article, we introduce the theory and instrumentation relevant to SERS induced by silicon dioxide (SiO2)-coated shell isolated gold nanoparticles (Au@SiO2) core?shell nanoclusters (NCs) and nanorods (NRs). We explain the synthetic methods used to generate Au@SiO2 core?shell NCs and NRs and show how they can be manipulated for SERS applications, including their use in biosensors that are able to quantitatively analyze small molecules and their roles in the structural identification of ?amorphous ultrathin solid-state film materials and in elucidating the interphase reactions between the electrode and electrolyte in lithium-ion (Li-ion) batteries. Our findings support the view that SERS techniques, used in conjunction with metallic NCs or NRs, can reduce the detection limits for target molecules and are, thus, applicable to future studies of nanoscale materials. Copyright 2014 IEEE.