Activated Sludge Models (ASMs) assume an unbiodegradable organic particulate fraction in the activated sludge, which is derived from the decay of active microorganisms in the sludge and/or introduced from wastewater. In this study, a seasonal change of such activated sludge constituents in a municipal wastewater treatment plant was monitored for 1.5 years. The chemical oxygen demand ratio of the unbiodegradable particulates to the sludge showed a sinusoidal pattern ranging from 40 to 65% along with the change of water temperature in the plant that affected the decay rate. The biogas production in a laboratory-scale anaerobic digestion (AD) process was also affected by the unbiodegradable fraction in the activated sludge fed. Based on the results a chemical pre-treatment using H2O2 was conducted on the digestate to convert the unbiodegradable fraction to a biodegradable one. Once the pre-treated digestate was returned to the digester, the methane conversion increased up to 80% which was about 2.4 times as much as that of the conventional AD process, whilst 96% of volatile solids in the activated sludge was digested. From the experiment, the additional route of the organic conversion processes for the inert fraction at the pre-treatment stage was modelled on the ASM platform with reasonable simulation accuracy.