Fermented foods represent a wide array of products with substantial cultural, ecological, and economic importance. Advancing research and innovation in this domain requires analytical techniques that are efficient, eco-friendly, and cost-effective. Volatile organic compounds (VOCs), which are generated as a result of microbial metabolism during fermentation, serve as indicators of bioprocess dynamics and are closely linked to sensory attributes. Monitoring these volatiles in real-time can reveal critical information regarding fermentation progress, product safety, and aromatic profiles. Direct-Injection Mass Spectrometry (DIMS) is a sustainable analytical method that facilitates rapid, high-sensitivity VOC detection without the need for labor-intensive preparation or separation procedures. This technique has proven effective in tracking fermentation-related microbial activities, even in microbiologically complex environments of alimentary interest. In this study, we present a series of case studies overviewing the use of DIMS in characterizing VOCs across diverse fermented matrices, including dairy (e.g., yoghurt, kefir), cereal-based items (e.g., sourdough), and fermented beverages (e.g., wine, beer, kombucha). FB and VC were supported by Investment 1.3 – Award Number: Project code PE00000003. GS and MG by Investment 1.4—D.D. 1032 17 June 2022, CN00000022] CN00000022] within the Agritech National Research Centre for Agricultural Technologies.