The fingerprinting of olive oil is a challenging task of interest for quality and authenticity assessment. Investigation of the volatile fraction is an informative and diagnostic tool for olive oil characterization and sensory evaluation; thus, the possibility to enhance the extractable information gaining a higher level of understanding is highly desirable. Headspace (HS) solid-phase microextraction (SPME) is the most applied technique for such a goal. However, a compromise between sensitivity and extraction time is usually needed to optimize the sample throughput, especially when a large number of samples are analyzed, as usually the case in cross-samples studies. Two novel approaches were investigated for enhancing the performance of HS-SPME, alone or incombination: multiple-cumulative HS-SPME and vacuum assisted HS-SPME. Both approaches provided a significant improvement in the extraction yield, in particular of semi-volatile compounds. Moreover, they provided more information in shorter sampling time, allowing a more comprehensive fingerprinting of the olive oil volatiles.