This work investigated the biosynthetic mechanism of lichenysin, the newly identified nonvolatile matrix component in Chinese liquors. Transcriptomes were analyzed in three producers, Bacillus licheniformis CGMCC 3961, 3962, and 3963, which were isolated from Maotai-flavor liquor-making process and produced 386.3, 553.5, and 795.2 μg/L lichenysin in a simulative liquor fermentation process. Lichenysin synthetase genes lchAA-AD in these three producers were expressed much more highly than those of the nonproducer B. licheniformis ATCC 14580 (>18.4-fold). In addition, ABC transporters were the most significant responsive metabolic pathway, and the expression levels of peptide transporter genes dppABCDE all increased more than 19.2-fold. When B. licheniformis CGMCC 3963 was cultured in synthetic medium, the expression of dppABCDE and lichenysin both increased with the addition of casein hydrolysate (containing various peptides). This indicated that peptide would act as a substrate for lichenysin synthesis. This work sheds new light on the mechanism for lichenysin biosynthesis.