Raman scattering measurements were conducted for a 4-aminobenzenethiol (4-ABT) monolayer assembled on a macroscopically smooth Au substrate. Although no peak was detected at the beginning, Raman peaks were distinctly observed by attaching Ag or An nanoparticles onto the 4-ABT monolayer (Ag(Au)@4-ABT/ Au(flat)). Considering the fact that no Raman signal is observed when Ag (Au) nanoparticles are adsorbed on a (4-aminophenyl)si lane monolayer assembled on a silicon wafer, the Raman spectrum observed for Ag(Au)@4-ABT/Au(flat) must be a surface-enhanced Raman scattering (SERS) spectrum, derived from the electromagnetic coupling of the localized surface plasmon of Ag (An) nanoparticles with the surface plasmon polariton of the underneath Au metal. The electromagnetic coupling responsible for SERS appeared to be governed more by the bulk An substrate than the sparsely distributed Ag or Au nanoparticles. The chemical enhancement appeared on the other hand to be derived more from the formation of Au-S bonds than any charge-transfer interaction between the protonated amine group and the Au or Ag nanoparticles. The enhancement factors derived from the attachment of a single Ag or Au nanoparticle onto 4-ABT on Au were estimated to be as large as 8.3 x 10(5) and 5.0 x 10(5), respectively, (for the ring 3 band (b(2)) near 1390 cm(-1)) in which a factor of similar to 10(2) was presumed to be due to the chemical effect, with the remaining contributed by the electromagnetic effect.