Olives (Olea europaea cv. Chondrolia) were stored under a CO2 atmosphere immediately after harvesting for a period of 12 days. Samples obtained at 24-h intervals were analyzed by HPLC to identify components that may reflect changes in the biochemical behavior of the tissue. Four substances were shown to undergo significant fluctuations during storage, while their evolution was found to be different in olives stored under CO2 from those stored under regular atmospheric conditions (control). On the basis of data provided by liquid chromatography-electrospray ionization mass spectrometry, these substances were tentatively identified as hydroxytyrosol glucoside, demethylated ligstroside aglycone, ibotalactone A methyl ester, and verbascoside. The data are discussed in relation to the effect of postharvest treatments of olives for purposes of manipulating their polyphenolic content and plausible development of novel debittering processes.