The requirement for developing an instrumental method for analysis of volatile compounds responsible for the aroma that supports the work of the sensory panel test of virgin olive oils is a matter of great importance. In this paper, five laboratories participated in a collaborative study within the EU H2020 OLEUM project to develop a peer interlaboratory study of a harmonized SPME-GC-MS method for determination of volatile compounds in virgin olive oil responsible for positive attributes (e.g. fruity) and the main sensory defects. Linearity (R2 > 0.94) and repeatability (mean relative standard deviation, RSD% = 7.60%) were satisfactory. Reproducibility results were uneven depending on the compound. The lowest RSD% values were found for (Z)-3-hexenyl acetate (19.19%), 1-hexanol (13.26%), and acetic acid (17.47%). The limits of quantification were <0.07 mg/kg for all compounds except for (E)-2-decenal and pentanoic acid. The study of different quantification methods revealed that the correction of the calibration curves using the internal standard led to a slightly worse repeatability, but better accuracy and reproducibility. The results obtained by five laboratories are preparatory towards a trial proper validation study, already planned in OLEUM project, involving external labs participating on a voluntary basis.