Surface-enhanced Raman spectra (SERS) of molecules separated by gas chromatography (GC) were measured off-line by condensing the analyte on a moving, liquid-nitrogen-cooled ZnSe window on which a 5 nm layer of silver had been formed by physical vapor deposition. After the components that eluted from the chromatograph had been deposited, the substrate was allowed to warm up to room temperature and transferred to the focus of a Raman microspectrometer where the spectrum of each component was measured. Band intensities in the spectrum of 3 ng of caffeine prepared in this way were approximately the same as in the spectrum of bulk caffeine. By making some logical assumptions, it was shown that identifiable GC/SERS spectra of 30 pg of many molecules could be measured over a 300 cm(-1) region in real-time and that if an optimized substrate were used the minimum identifiable quantity could be reduced to 1 pg or less.