This work aimed to assess microbial inoculants (Lactiplantibacillus plantarum and Lentilactobacillus buchneri), chemical additives (natamycin and hexanoic acid), and their combination on fermentation characteristics and aerobic stability in total mixed ration (TMR) silage. The TMR consisted of 30% water bamboo shell (WBS), 10% alfalfa, 20% rice straw, and 40% concentrate. There were six treatments as follows: (1) deionized water (control, CON). (2) lactic acid bacteria (Lactiplantibacillus plantarum + Lentilactobacillus buchneri; LPB, 1 × 106 cfu/g FW). (3) natamycin (NT, 0.02 g/kg FW). (4) hexanoic acid (HA, 0.02 g/kg FW). (5) lactic acid bacteria + natamycin (SLNT, 0.02 g/kg FW). (6) lactic acid bacteria + hexanoic acid (SLHA, 0.02 g/kg FW). After fermentation, laboratory silos (10 L) were opened to assess fermentation quality, followed by a 6-day aerobic stability test. The results showed that all silages were well fermented with high lactic acid (LA) content, low ammonia nitrogen (NH3-N), and negligible butyric acid (BA) levels. Among all silages, SLNT silage exhibited the greatest LA, acetic acid (AA) levels, LAB counts, and the lowest pH and NH3-N. For aerobic stability, all additives significantly (p < 0.05) enhanced aerobic stability, delayed (p < 0.05) the decrease in LA and water-soluble carbohydrates (WSC) and the increase in pH, and significantly (p < 0.05) minimized yeast proliferation. The SLNT silage showed the best aerobic stability, with SLHA, NT, HA, and LPB following. In conclusion, SLNT is recommended as the optimal additive in improving the fermentation quality and aerobic stability of TMR silage, with SLHA, NT, HA, and LPB following.