Silver nanoparticles (Ag NPs) were chemically deposited on silicon nanowires (SiNWs), prepared using the vapor-liquid-solid (VLS) growth mechanism, using an in situ electroless metal deposition technique. The resulting SiNWs/Ag NPs composite interfaces showed large Raman scattering enhancement for rhodamine 6G (R6G) with a detection limit of 10(-14) M and an enhancement factor of 2.3 x 10(8). This large enhancement factor was attributed to the presence of "hot" spots on the SiNWs/Ag NPs substrate.