In this work surface-enhanced resonance Raman spectroscopic experiments have demonstrated that metallic single-walled carbon nanotubes can be used as chemical assemblies between the pyrene analyte and the silver colloidal surface. Pyrene has been detected at concentrations lower than 10-9 M by use of the 514.5 nm excitation laser line. A charge transfer from the surface to the nanotube characterizes the nanotube-silver surface interaction. The pyrene-nanotube interaction occurs through a π-π electronic stacking. Extended Hückel calculations based on a simplified molecular model for the analyte/nanotube/surface system support the experimental conclusions. The nanotube-pyrene distance is 3.4 Å, and the most probable orientation for pyrene is confirmed to be plane parallel to the nanotube surface. An energy transfer from the silver surface to the nanotube/analyte system is verified.