The ternary pH buffer system with ammonia-carbonates-volatile fatty acids (VFAs) is essential to anaerobes for bioenergy recovery via anaerobic digestion (AD). However, ammonia and VFAs are recognized as potential inhibitors that depress methanogenesis. In this study, biochemical conversion and the microbial community in batch AD at total solid (TS) from 4% to 14% were investigated to reveal their response to the ternary pH buffer system. The rapid ammonia release, probably promoted by Anaerosphaera and Eubacterium inferred from the concurrent peak of their relative abundance, triggered total ammonia (TAN) inhibition with the accumulation of VFAs in the start-up stage of high solid AD (HSAD, TS â„ 8%). Along with evolution of the microbial community to resist high TAN and VFAs, methanogenesis recovered with improved degradation of VFAs and reduction of COD. When exposed to 3500 mg·N·Lâ1 TAN at 8% TS, aceticlastic Methanosarcina became dominant first and then together with hydrogenotrophic Methanoculleus, achieved the optimal biochemical conversion. While in HSAD at 11â14% TS, the main pathway of methanogenesis appeared to have shifted from the aceticlastic pathway to the hydrogenotrophic pathway, as inferred by changes in the relative abundance of methanogens, and this could have been induced by the increasing concentration of high free ammonia (FAN, â„588 mg·N·Lâ1). Although the anaerobes had acclimatized to high TAN, the propionate-oxidizing bacteria and acetate-oxidizing bacteria might have again been inhibited by high FAN, frustrating the H2 supply for FAN-tolerant Methanoculleus and causing an 8.2â11.3% depression of COD reduction (mainly propionate residual).