Lignite is difficult to degrade, thus stimulation of the autochthonous lignite microflora and introduction of additional microorganisms are required for lignite decomposition. Here, a packed bed reactor, filled with lignite samples from the Konin region (central Poland) was supplied continuously with M9 medium, supplemented with molasses (a by-product from the sugar industry), for 124 days to stimulate the autochthonous lignite microflora. Acidic fermentation of molasses was observed in the bioreactor. The simultaneous decomposition of lignite occurred under this acidic molasses fermentation condition. Our results show decay of free (non-bound) organic compounds during anaerobic lignite biodegradation. The concentrations of n-alkanes, n-alkanols, n-alkanoic acids, diterpenoids, triterpenoids and steroids present in non-biodegraded samples decreased significantly (some compounds to zero) during biodegradation. Interestingly, other compound classes like phenols, ketones and certain organic compounds increased. We interpret this phenomenon as a gradual decomposition of polymers, lignin and cellulose, present in the lignite. These changes resulted from microbial activity since they were not observed in pure solutions of short-chain fatty acids. The 16SrRNA profiling of the microbial community selected in the bioreactor revealed that the dominant bacteria belonged to the Firmicutes, Actinobacteria, Proteobacteria and Bacteroidetes, furthermore representatives of 16 other phyla were also found. All the known taxa of lignocellulolytic bacteria were represented in the microbial community. Synergistic relations between bacteria fermenting molasses and bacteria degrading lignite are assumed. The results confirm lignin degradation in acidic medium by bacteria under anaerobic conditions.