The utility of volatile compounds to explain virgin olive oil aroma descriptors is fully accepted and demanded by the olive oil sector. However, the methodology, and particularly the kind of detector to be used, is a matter of discussion because the high number of volatiles and their different nature. The SPME-GC-MS method has recently been validated for the most relevant volatiles but SPME-GC-FID method still needs to be validated to evaluate its performance in this application. A comparison between these two GC methods in determining 26 volatiles has been carried out in terms of analytical quality parameters (repeatability, intermediate precision, calibration curves, limits of detection and quantification, linear working ranges, selectivity and sensitivity). Good selectivity, linearity and higher upper values of the working range are the main advantages of SPME-GC-FID versus low bottom values of working ranges, better sensitivity and lower limits of detection and quantification of SPME-GC-MS. The limit of blank associated to each individual volatile was also determined and it allowed perfecting the empirical limit of detection. This procedure was carried out for SPME-GC-FID, which resulted in 21 volatiles with empirical limits of detections lower than their odor thresholds, and hence they can be used as markers of virgin olive oil sensory descriptors. Finally, with all the analytical quality parameters checked, a practical example of the ability of the volatiles quantified by SPME-GC-FID to discriminate the different categories (extra-virgin, virgin and lampante) and their main aroma descriptors is also provided.