The utility of polymer-metal nanocomposite thin films with in situ generated silver nanoparticles as substrates for surface-enhanced Raman scattering (SERS) is demonstrated. Thin films of poly(vinyl alcohol) and poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) containing Ag nanoparticles generated in situ through thermal annealing and photoirradiation, respectively (Ag-PVA and Ag-PVVV), are investigated as potential SERS substrates using 4-aminothiophenol and rhodamine 6G as probe molecules. The fabrication protocols are extremely simple and the materials inexpensive. The Ag-PVA substrate is found to produce Raman spectral enhancement factors of similar to 10(6), whereas Ag-PVVV, a novel nanocomposite thin film developed in the present study, provides enhancement factors of similar to 10(7). A unique advantage of these nanocomposite films is demonstrated by fabricating them by the in situ process as a thin coating inside glass capillaries and using these disposable SERS substrates for the sensitive detection of the probe molecules. The thin film substrates prepared on glass plates and capillaries facilitate convenient sample preparation for recording the Raman spectra and provide strongly enhanced spectra with high reproducibility, allowing picomols of the analytes to be detected. These aspects combined with the ease of fabrication and low cost of these in situ fabricated nanocomposite thin films make them highly attractive SERS substrates.