The urbanization-driven surge in kitchen waste necessitates optimized dry anaerobic digestion (DAD; total solids > 15%). Despite its valorization potential, this technology requires efficiency improvements due to mass transfer constraints. This study evaluated TS effects (15%, 20%, or 25%) on methane production. The TS = 20% system achieved peak cumulative methane yield (405.73 ± 11.71 mL/gVS), exceeding TS = 15% (348.09 ± 12.19 mL/gVS) and TS = 25% (293.08 ± 3.55 mL/gVS). This optimization was attributable to synergistic maintenance of metabolic equilibrium through autonomous pH recovery, rapid VFAs degradation, and enhanced TAN tolerance. Conversely, TS = 25% exhibited impaired mass transfer efficiency under high solids, causing VFAs accumulation, ammonia toxicity, and progressive pH decline to 7.5, indicating system destabilization. Organic degradation analysis confirmed superior conversion efficiency in TS = 20% through dynamic SPS–SPN equilibrium. Microbial analysis revealed enhanced metabolic efficiency via synergistic interactions between acetoclastic and hydrogenotrophic methanogens in TS = 20%. This research provides technical parameters for optimizing methane production in kitchen waste DAD systems.