A large volume-headspace apparatus that permits the heating of pottery fragments for direct analysis by gas chromatography/mass spectrometry is described here. A series of fermented-corn beverages were produced in modern clay pots and the pots were sampled to develop organic-species profiles for comparison with fragments of ancient pottery. Brewing pots from the Tarahumara of northern Mexico, a tribe that regularly uses corn kernels to ferment a weak beer, were also examined for volatile residues and organic-species profiles were generated. Finally, organic species were generated from ancient potsherds from an archaeological site and compared with the modern spectra. The datasets yielded similar organic species, many of which were identified by computer matching of the resulting mass spectra with the NIST mass spectral library. Additional analyses are now underway to highlight patterns of organic species common to all the spectra. This presentation demonstrates the utility of GC/MS for detecting fermentation residues in the fabric of unglazed archaeological ceramics after centuries of burial. This, in turn, opens unexpected new doors for understanding the human past by means of GC/MS analyses.