A low temperature plasma (LTP) ionization interface between a gas chromatograph (GC) and an atmospheric pressure inlet mass spectrometer, was constructed. This enabled time-of-flight mass spectrometric detection of GC-eluting compounds. The performance of the setup was evaluated by injection of mixtures of common volatile organic compounds. Amounts down to ca. 0.5 ng (on column) could be detected for most compounds and with a chromatographic performance comparable to that of GC/EIMS. In the positive mode, LTP ionization resulted in a compound specific formation of molecular ions M(+•), protonated molecules [M + H](+), and adduct ions such as [(M + O) + H](+) and [M + NO](+). The ion patterns seemed unique for each of the analyzed compound classes and can therefore be useful for identification of functional groups. A total of 20 different compounds within 8 functional groups were analyzed.