The localized surface plasmon resonance of plasmonic nanoparticles (NPs) can be coupled with a noble metal substrate (S) to induce a localized augmented electric field (E-field) concentrated at the NP-S gap. Herein, we analyzed the fundamental near-field properties of metal NPs on diverse substrates numerically (using the 3D finite-difference time-domain method) and experimentally [using surface-enhanced Raman scattering (SERS)]. We systematically examined the effects of plasmonic NPs on noble metals (Ag and Au), non-noble metals (Al, Ti, Cu, Fe, and Ni), semiconductors (Si and Ge), and dielectrics (TiO2, ZnO, and SiO2) as substrates. For the AgNPs, the Al (11,664 times) and Si (3969 times) substrates produced considerable E-field enhancements, with Al in particular generating a tremendous E-field enhancement comparable in intensity to that induced by a Ag (28,224 times) substrate. Notably, we found that a superior metallic character of the substrate gave rise to easier induction of image charges within the metal substrate, resulting in a greater E-field at the NP-S gap; on the other hand, the larger the permittivity of the nonmetal substrate, the greater the ability of the substrate to store an image charge distribution, resulting in stronger coupling to the charges of localized surface plasmon resonance oscillation on the metal NP. Furthermore, we measured the SERS spectra of rhodamine 6G (a commonly used Raman spectral probe), histamine (a biogenic amine used as a food freshness indicator), creatinine (a kidney health indicator), and tert-butylbenzene [an extreme ultraviolet (EUV) lithography contaminant] on AgNP-immobilized Al and Si substrates to demonstrate the wide range of potential applications. Finally, the NP-S gap hotspots appear to be widely applicable as an ultrasensitive SERS platform (similar to single-molecule level), especially when used as a powerful analytical tool for the detection of residual contaminants on versatile substrates.