Silage exposed to air is prone to deterioration and production of unpleasant volatile chemicals that can seriously affect livestock intake and health. The aim of this study was to investigate the effects of (LP), (LB), and a combination of LP and LB (PB) on the quality, microbial community and volatile chemicals of silage at 0, 4, and 8 days after aerobic exposure. During aerobic exposure, LP had higher WSC and LA contents but had the least aerobic stability, with more harmful microorganisms such as and and produced more volatile chemicals such as Isospathulenol and 2-Furancarbinol. LB slowed down the rise in pH, produced more acetic acid and effectively improved aerobic stability, while the effect of these two additives combined was intermediate between that of each additive alone. Correlation analysis showed that , , , and were associated with aerobic deterioration, and , , , and were associated with volatile chemicals. In conclusion, LB preserved the quality of silage during aerobic exposure, while LP accelerated aerobic deterioration.