The variety- and pre-fermentation-related volatile compounds of 'Fernão-Pires' (FP) white grape berries were analyzed during ripening by headspace-solid phase microextraction (HS-SPME) coupled to gas chromatography-quadrupole mass spectrometry (GC-qMS). A preliminary step, in which the grapes were crushed and macerated before HS-SPME analyses, was used. The sampling started at véraison (beginning of berry ripening) and was carried on during 5 weeks in two different vineyards. Sixteen terpenoids, two C13 norisoprenoids, two aromatic alcohols, two C6 aldehydes, and three C6 alcohols were identified. The amount of all volatiles increased since véraison towards day 20. A sharp decrease was observed after this day. The maximum amount of varietal volatile compounds was coincident with the harvesting day for white table wine production defined by the ratio sugar/acid content. The varietal volatile evolution observed for FP grapes shows that the maximum amount of volatiles occurs only in a very short period. As a consequence, the establishment of the optimum moment for harvesting of FP white variety, based on its volatile content, deserves higher accuracy than that necessary for all other already studied grapes. This work also evidences that the analysis of the evolution of the terpenoids with higher GC peak area can represent the evolution of all varietal compounds. For FP grapes, this work shows that the screening of linalool, alpha-terpineol, and geraniol during ripening can be used to define the evolution profile of the varietal volatile compounds.