Abstract Biogas utilization in fuel cell technology and hydrogen generation is a modern and economically viable approach. A pretreatment step prior to anaerobic digestion (AD) is obligatory to increase the hydrolysis, solubilize the complex matter present in organic fraction of municipal solid waste (OFMSW) and to achieve higher yield of biogas. This study was intended to find out the effects of thermal, chemical and thermochemical pretreatments on the properties and structure of OFMSW and also on biogas production. There was an increase in chemical oxygen demand of 6.87, 1.61 and 11.60% for thermal, chemical and thermochemical pretreatments, respectively. Also, the content of volatile solids was reduced by 2.36% by thermochemical pretreatment. FTIR, XRD and SEM analysis revealed that these pretreatments also caused chemical and morphological changes on the substrate, as a result reduced its crystallinity and enhanced the rate of hydrolysis. A significant increase of 54% in biogas yield was achieved after thermochemical pretreatment in comparison to untreated OFMSW sample.