The sensory perception of virgin olive oil is complex and produced mainly by phenols and volatiles. These compounds are affected by the interaction with other components of the oil matrix and by biological factors. The aim of the work was to study the saliva effect and/or the presence of phenols on the release of 12 volatiles, using different olive oil matrices and volatile concentrations, and applying Solid Phase Microextration-Gas Chromatography-Flame Ionization Detection, Proton Transfer Reaction-Mass Spectrometry and sensory analysis. The volatile concentrations in the headspace showed significant differences (p < 0.05) between the different matrices, being easily detected the effect exerted by phenols and biological components from 3.8 mg/Kg. The results showed that the presence of unsaturation in the volatile molecules affect their release, being lower the concentration of saturated volatiles released in presence of phenols. All the compounds were in higher concentration in the headspace of the olive oil-phenol-saliva matrix.