High-solids anaerobic digestion of sewage sludge was a promising process, but high solid concentration negatively influenced methane production. The influencing mechanism was systematically analyzed in this study through a series of static anaerobic digestion experiments at total solids (TS) contents of 3%–15%. The results showed that TS 6% was the boundary between low-solids and high-solids anaerobic digestion, and the accumulative methane yield decreased exponentially when TS increased from 6% to 15%. The performance of anaerobic digestion was directly determined by the efficiency of mass transfer, and the relation between methane yield and sludge diffusive coefficients was well described by a power function. Thus, the increasing TS resulted in an exponential increase in sludge viscosity but an exponential decrease in diffusive coefficient. The blocked mass transfer led to the accumulation of volatile fatty acids (VFAs) and free ammonia. Acetic metabolism was the main process, whereas butyric and propionic metabolisms occurred at the initial stage of high-solids anaerobic digestion. The concentration of VFAs reached the maximum at the initial stage, which were still lower than the threshold influencing methanogens. The concentration of free ammonia increased gradually, and the methanogenesis was inhibited when free ammonia nitrogen exceeded 50 mg·L . Consequently, the deterioration of high-solids anaerobic digestion was related to the blocked mass transfer and the resulting ammonia accumulation.