The volatile components of roasted coffee were separated into basic and neutral components and analyzed on a 185 m × 0.31 mm i.d. glass capillary column coupled to a mass spectrometer. Seventeen alkylated five- and six-membered alicyclic pyrazines are reported for the first time in roasted coffee. The identities of bicyclic pyrazines were confirmed by direct comparison of their mass spectral and gas chromatographic retention data with those of authentic samples and with spectra given in the literature. Possible precursors of the bicyclic pyrazine compounds are discussed. The principal mass spectrometric fragmentation pathways of cyclopentapyrazines and tetrahydroquinoxalines are demonstrated.