The purpose of this study was to investigate the effect of different additives on the microbial composition, fermentation quality, and bacterial community structure of big-bale Leymus chinensis silage. An experiment was set up with four treatment groups: a control (C) group, Lacticaseibacillus rhamnosus (L) group, molasses (M) group, and L. rhamnosus + molasses (LM) group, with three replications per group, and L. chinensis silages were fermented for 20 and 40 days. The lactic acid, acetic acid, 1,2-propanediol, and propionic acid contents increased, and pH, butyric acid, 1-propanol, and ethanol contents decreased in the L, M, and LM groups compared to the C group. In the LM group, the number of lactic acid bacteria was the highest, while the pH was the lowest. Enterobacter and Paucibacter were the main dominant genera in the C group. The addition of L. rhamnosus and molasses increased the relative abundance of Lactobacillus, Weissella, and Enterococcus. Lactobacillus abundance correlated positively (p < 0.01) with Lactococcus, Enterococcus, and Weissella and correlated negatively with Enterobacter and Paucibacter. Conversely, Enterobacter and Paucibacter showed a strong positive correlation (p < 0.01, R = 0.55) during fermentation. Lactobacillus, Enterococcus, and Weissella were positively associated (p < 0.01) with acetic and lactic acid levels, while Enterobacter abundance was correlated positively (p < 0.05, R = 0.43) with 1,2-propanediol content. In summary, the addition of both L. rhamnosus and molasses improved the fermentation quality and bacterial community structure of big-bale L. chinensis silage. In addition to inhibiting harmful microorganisms, this combination improved the fermentation products of big-bale L. chinensis silage through microbial regulation.