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Reuse and recycling are preferred strategies in waste management to ensure the high position of waste resources in the waste management hierarchy. However, challenges are still pronounced in many developing countries, where disposal as a final solution is prevalent, particularly for municipal solid waste. On the other hand, refuse-derived fuel as a means of energy recovery provides a sustainable option for managing mixed, contaminated and residual municipal solid waste (MSW). This study provides one of the earliest assessments of refuse-derived fuel (RDF) from MSW in Ghana through a case study in the cities of Accra and Kumasi. The residual/reject fractions (RFs) of MSW material recovery were characterized for thermochemical energy purposes. The studied materials had the potential to be used as RDF. The combustible portions from the residual fractions formed good alternative fuel, RDF, under the class I, II-III classification of the EN 15359:2011 standards. The RDF from only combustible mixed materials such as plastics, paper and wood recorded a significant increase in the lower heating value (28.66–30.24 MJ/kg) to the mass RF, with the presence of organics (19.73 to 23.75 MJ/kg). The chlorine and heavy metal content met the limits set by various standards. An annual RDF production of 12 to 57 kilotons is possible from the two cities. This can offset 10–30% of the present industrial coal consumption, to about 180 kiloton/yr CO2 eq emissions and a net cost saving of USD 8.7 million per year. The market for RDF as an industrial alternative fuel is developing in Ghana and similar jurisdictions in this context. Therefore, this study provides insights into the potential for RDF in integrated waste management system implementation for socioeconomic and environmental benefits. This supports efforts towards achieving the Sustainable Development Goals (SDGs) and a circular economy. [ABSTRACT FROM AUTHOR]