This study addresses the characterization of volatile organic compounds (VOCs) emitted by samples of 13 different wood species, belonging to both softwoods and hardwoods groups, regularly measured at different intervals of time, after the first measurement on green wood. The same wood specimens were subjected to several cycles of water desorption and adsorption, assuming that moisture variation might play a role in both the formation and emission of VOCs. Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-TOF-MS) was used as a tool to characterize the emission of VOCs. Coupled with a multivariate class-modelling approach, this tool was able to discriminate between groups (softwood and hardwood) and in some cases between different species. However, results showed that the discriminant capacity of VOCs emission to separate species and families rapidly decreases after the first cycles of moisture variation in wood. The green wood was characterized by a richness of volatile compounds, whereas, after only the first dry cycle, wood emitted a more restricted group of compounds. We hypothesized that most of these VOCs might have originated from structural changes and degradation processes that involve the main polymers (particularly hemicellulose) constituting the cell wall of wooden cells. The results obtained are in agreement with the physical and chemical modification processes that characterize wood ageing.