Phlebopus bruchii is a pricy edible fungus sold in the regional markets of Argentina. This mushroom has a strong boletoid aroma; however, the organoleptic attributes of its volatile organic compounds are unknown. The internal transcribed spacer nrDNA region (ITS) was used for phylogenetic reconstruction based on maximum likelihood (ML) analysis. To obtain the volatile organic compounds (VOCs), a solid-phase microextraction coupled with a gas chromatography/mass spectrometry analysis (SPME–GC–MS) was used to identify the VOC profile of the samples based on their maturity (immature vs. mature) stages and if they were fresh or dried. Among the latter category, we also analyzed VOCs in recently dried samples and after 12 months of dehydration. Up to 65 VOCs were obtained. The most abundant and total VOCs were analyzed with principal component analysis (PCA), showing some notorious changes among the aromatic profiles produced before and after the drying process, and throughout the evolution of those volatile compounds during the commercial shelf-life of the dried mushrooms.