A mono-6-thio-beta-cyclodextrin-modified silver film was synthesized via galvanic displacement on copper foil. The prepared silver films could enrich non-polar polychlorinated biphenyls (PCBs) molecules from hydrophilic phase using thiolate beta-cyclodextrins (SH-beta-CDs) as receptors. The components of as-prepared Ag-coated-Cu (Ag-Cu) film were confirmed by powder X-ray diffraction (XRD). Both surface-enhanced Raman spectroscopy (SERS) and energy dispersive X-ray spectroscopy (EDS) measurements gave strong evidences that the thiolated beta-cyclodextrins (SH-beta-CDs) had been immobilized on the surface of silver film. Compared to the substrates prepared in the absence of sH-beta-co, the surface morphology of the CD-modified Ag films was obviously changed. The interfacial enrichment and the capability of substrates to form inclusion complexes with PCBs molecules were tested by using PCB-15 (4,4'-dichlorobiphenyl) as the probe molecules via SERS technique. The measured SERS spectra could distinguish the PCB-15 molecules at micro-molar level according to the most intense CCC bending in-plane mode of PCBs. The enhancement factor (EF) of the SERS substrates for PCB-15 was 1.2 x 10(5), which was comparable with a number of previous reports. (C) 2011 Elsevier Inc. All rights reserved.