The headspace volatile organic compound (VOC) fingerprints (volatilome) of French wine brandies were investigated by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS). Protonated ethanol chemical ionization was used with dedicated experimental conditions that were previously validated for model wines. These included a reference vial containing a hydro-alcoholic solution with the same ethanol content (20% v/v) as the diluted sample spirits, which was used to establish steady-state ionization conditions. A low electric field strength to number density ratio E/N (85 Td) was used in the drift tube in order to limit the fragmentation of the protonated analytes. The obtained headspace fingerprints were used to investigate the origin of French brandies produced within a limited geographic production area. Brandies of two different vintages (one freshly distilled and one aged for 14 years in French oak barrels) were successfully classified according to their growth areas using unsupervised (principal component analysis, PCA) and supervised (partial least squares regression discriminant analysis, PLS-DA) multivariate analyses. The models obtained by PLS-DA allowed the identification of discriminant volatile compounds that were mainly characterised as key aroma compounds of wine brandies. The discrimination was supported by sensory evaluation conducted with free sorting tasks. The results showed that this ethanol ionization method was suitable for direct headspace analysis of brandies. They also demonstrated its ability to distinguish French brandies according to their growth areas, and this effect on brandy VOC composition was confirmed at a perceptive level.