A comparison among different sampling methods (3 types of sorbent tubes and polymeric bags) commonly adopted in chemical analyses of odorous emissions was performed. To investigate the different performances, a lignocellulosic biomass storage plant was selected to obtain preliminary information about the chemical nature of odorous emissions. Samples of odorous emissions were collected at different biomass piles and analysed by dynamic olfactometry and TD-GC-MS. By comparing the two adopted sampling methods (tubes and bags), different performances are shown, depending on their specificity. By the comparison among the three types of sorbent tubes (Multi-sorbent bed (Carbotrap, Carbopack X and Carboxen 569), Tenax and Sulphur), Sulphur and Multi-sorbent bed present similar performance, while Tenax TA tubes show a different trend in terms of type and numerosity of detected compounds. In addition, from the comparison between tubes and polymeric bags, the number and types of compounds detected in bags are more comparable to those observed in the Multi-sorbent bed and Sulphur tubes. However, a difference between the two methods appears, especially in the detection of low-molecular weight organic compounds. In this study, it is possible to highlight that, due to the complexity of odorous emissions, the selection of the sampling material may affect the obtained chemical results. The detection of different classes of compounds, is a crucial point, to obtaining the most complete characterization of mixtures and comparing the chemical profile with olfactometric results: care must be taken in the choice of sampling material and procedure.