Volatile phenols are strong odorants produced by microbial activity and reported in several foods, but very scarce information is available on their presence in virgin olive oils (VOOs) and on their relation with VOO chemical and sensory quality. In the present paper, a factorial experimental design was applied for the development of a suitable solid-phase microextraction-gas chromatography/mass spectrometry (SPME-GC/MS) analytical method for the analysis of volatile phenols in olive oil. The memory effects demonstrated by SPME fibres required the optimization of desorption conditions to minimize experimental errors. A series of nine volatile phenols were identified and quantified for the first time in VOOs by analyzing samples with distinct off-flavours. Their limits of detection and quantification (microg/kg) were largely below the odour detection thresholds (ODTs) calculated in this study (mg/kg), confirming the capacity of the technique to assess the target compounds at early stages of the oil sensory alteration. The odour activity values (OAVs) of volatile phenols were calculated in VOOs facilitating a first assessment of their potential importance in the aroma of the product.