The deinking pulp (DIP) is a main resource for paper making, and the wastewater from DIP process needs to be treated. Anaerobic biochemical technique has been widely applied in DIP wastewater treatment, due to the remarkable capability in reducing high chemical oxygen demand (COD). In this study, a mathematical simulation model was established to investigate the performance of a full-scale anaerobic biochemical system for treating DIP wastewater. The model was based on Anaerobic Digestion Model No. 1 (ADM1), which was modified according to the specific anaerobic digestion process for DIP wastewater treatment. The hydrodynamic behavior of a full-scale anaerobic biochemical system was considered in this model. The characteristics of the influent DIP wastewater were assessed, and then, the substrate COD proportion was divided successfully for the necessity of ADM1 applying. The Monte Carlo technique was implemented to distinguish the most sensitive parameters that influenced the model output indicators comprising effluent COD and biogas production. The sensitive parameters were estimated and optimized. The optimized value of k_m_pro is 12.02, K_S_pro is 0.35, k_m_ac is 4.26, K_S_ac is 0.26, k_m_h2 is 16.62, and K_S_h2 is 3.21 × 10–5. The model was calibrated with 150 days operation values measured in the field. The subsequent 100 days on-site values were used to validate the model, and the results obtained by the simulations were in good agreement. This study provides a meaningful and theoretical model guidance for full-scale wastewater anaerobic biochemical treatment simulation.