Analysis of volatile organic compounds (VOCs) from saliva, to aid disease diagnoses, has received little attention. This work aims to address the paucity of information on saliva volatiles and includes a database of newly identified compounds whilst incorporating a review of the literature. The volatile constituents in the headspace of whole saliva obtained from ten healthy individuals were examined in a longitudinal study over a period of ten days using headspace-trap gas chromatography–mass spectrometry (HS-trap/GC-MS). A total of 317 compounds (268 identified) were found and compared across subjects and between samples with 34 VOCs being present in all 100 samples. The average number of compounds per subject ranged from 121 to 150 over a 10 day period and was fairly consistent for a particular individual (s.d. ranged from 3–15). However, the number of compounds present in an individual on all ten days was substantially lower ranging between 65 and 109, showing that there is significant daily variation in salivary composition. A core group of ubiquitous VOCs were found with the remaining VOCs showing significant intra and inter individual variability. Saliva VOCs have been found to be readily analysed using the HS-trap technique and studies on the VOCs from healthy individuals should be of utility for comparison with VOCs analysed from samples from diseased groups.