The Anaerobic Digestion Model No. 1 (ADM1) was employed to simulate methane (CH4) production in an anaerobic reactor (AR), and the associated bench-scale biochemical methane potential (BMP) assay, having sewage sludge (SWS) from a municipal wastewater treatment plant (WWTP) as feedstock. The SWS presented the following physical-chemical characteristics: pH (7.4–7.6), alkalinity (2,382 ± 100 mg CaCO3 L−1), tCOD (21,903 ± 1,000 mg L−1), TOC (895 ± 100 mg L−1), TS, TVS, and VSS (2.0%, 1.1%, and 0.8%, respectively). The BMP assay was conducted in six replicates under anaerobic mesophilic conditions (37 ± 0.1°C) for 11 days with a CH4 yield registered of 137.6 ± 6.39 NmL CH4 or 124 ± 6.72 CH4 g−1 VS−1. When the results obtained with the BMP bench-scale reactors were compared to the output generated with computational data by the ADM1 model having as input data the same initial sewage tCOD, similar cumulative CH4 production curves were obtained, indicating the accuracy of the ADM1 model. This approach allowed the characterization of the sludge and estimation of its biogas production potential. The combination of BMP assays, experimental data, and ADM1 model simulations provided a framework for studying anaerobic digestion (AD) processes.