Biochemical methane potential tests and lab-scale continuous experiments were conducted to improve the yield and energy efficiency of anaerobic digestion through thermal hydrolysis pre-treatment. Methane generation, yield, and solubilization efficiency were evaluated through lab-scale tests. The pre-treated samples presented 50% biodegradability at 140 °C and 61.5% biodegradability at 165 °C. The increase in biodegradability was insignificant at 165 °C or higher temperature, and it was confirmed that the optimum conditions were achieved at 165 °C and 20 min of solubilization. The lab-scale continuous experiments confirmed that polymers were decomposed into low-molecular-weight compounds due to thermal hydrolysis, and pH decreased. NH4HCO3 produced by thermal hydrolysis acted as an alkali to enable a more stable operation compared to that before thermal hydrolysis. Total chemical oxygen demand as chromium (TCODCr) and soluble chemical oxygen demand as chromium (SCODCr) indicated 35.4% and 23.1% removal efficiency in terms of organic matter removal, respectively. Methane yield was approximately 0.35 kg m−3 at 2.0–4.0 kg (m3 d)−1 and 0.26 kg m−3 at 5.0 kg (m3 d)−1. The solubilization rate of 40.9% by thermal hydrolysis was confirmed through the lab-scale tests to determine its full-scale applicability.