The coupling of Solid-Phase Microextraction (SPME) technology with gas chromatography (GC) has a well-established and successful history. Traditionally, SPME fibers have been the most popular form thanks to their versatility and the ease with which they can be fully automated. However, alternative geometries for SPME have been developed over the years, beginning with Stir Bar Sorptive Extraction (SBSE) and later evolving into Thin-Film SPME (TF-SPME) devices. Each of these formats offers distinct advantages and disadvantages, which are explored in this study. The primary objective of this study was to comprehensively compare available forms of SPME devices, with a special focus on the advantages of TF-SPME, a novel microextraction method particularly suited for the analysis of odorants in food. The study involved analyzing a standard mixture of 11 key food odorants, representing a range of polarities, to evaluate the efficiency of TF-SPME devices in terms of the number of analytes extracted. Furthermore, four types of TF-SPME devices were compared against each other in both standard mixtures and actual food samples. The final stage of the study employed GCxGC-ToFMS analysis to showcase the potential of the most efficient HLB-TF-SPME device in the non-targeted analysis of complex samples, exemplified by unfiltered wheat beer. This analysis demonstrated the significant capability of HLB-TF-SPME in capturing and identifying a wide range of volatile compounds in complex matrices.