Representative organic vapors have been introduced into the flowing afterglow of a low power (<5 W) dc-glow discharge, coupled to a quadrupole mass spectrometer. When a positive bias was applied to the ion sampling orifice, the very surprising result was that molecular mass spectra were obtained with a high sensitivity. When a negative bias was applied to the ion sampling orifice, fragmentation of the analyte was observed with an increase in the extent of ion dissociation as the voltage was increased. The breakdown pattern is compound-specific and would be useful in confirming the identity of an unknown sample. When combined with chromatographic separation, the FFGD-MS technique could be used for chemical speciation studies at the sub-picogram level.