Volatile compounds of roasted barley used in the production of barley coffee, the most common coffee substitute, were analysed by using solid-phase microextraction (SPME) followed by GC-MS and comprehensive GC x GC-TOF-MS, respectively. The optimised SPME extraction conditions in terms of selection of the fibre coating, extraction time and extraction temperature allowed to obtain the highest GC response, thus enhancing the identification capabilities of the developed method. As for the SPME-GC x GC-TOF-MS analysis, 64 compounds with similarity, reverse and probability values above 800, 900 and 6000, respectively, were identified, by using a polar x apolar column set combination; in contrast, GC-MS was able to identify a lower number of compounds, i.e. 40 volatiles.