The principal challenge in monitoring anaerobic digestion (AD) processes lies in the fact that conventional operational parameters (pH, volatile fatty acids, etc.) frequently lag behind the actual microbial performance. This study proposes microbial volatile organic compounds (mVOCs) as a novel indicator reflecting the species-specific characteristics of microorganisms and evaluates their ability to indicate the stability of AD processes in response to organic loading rate (OLR) perturbations. Both gradual and pulsed increases in OLR concentration resulted in an instantaneous change in production, which was also reflected in the variation of mVOCs. Furthermore, alkanes, alkenes, alcohols, aldehydes, ketones, and aromatic compounds exhibited a more pronounced response to OLR perturbations. Additionally, these mVOCs presented a strong co-occurrence with specific bacterial genera (Syntrophomonas, Defluviitoga, and Fastidiosipila) and archaeal genera (Methanobacterium, Methanoculleus, and Methanosarcina), thus positioning them as crucial producers of mVOCs. This suggests that mVOCs could function as biochemical indicators of AD performance and facilitate the understanding of what mVOCs are produced, and who the contributing microorganisms are. Further research is required to elucidate the resolution of mVOCs regarding other AD process perturbations, as well as to establish the optimal measurement frequencies and reference values.