Objectives: This study aims to assess the potential of municipal solid waste (MSW)-derived solid bio-fuels as sustainable alternatives to fossil fuels. It focuses on evaluating their physical characteristics, calorific values, and flue gas emission profiles to determine their suitability for clean energy applications. Theoretical Framework: Grounded in the waste-to-energy paradigm, this review draws upon concepts of resource valorization, sustainable energy transition, and environmental management. It examines how transforming heterogeneous MSW streams into solid bio-fuels aligns with global efforts to reduce landfill burden and carbon emissions. Method: A systematic review of peer-reviewed literature was conducted using scientific databases. The analysis covered studies involving MSW briquettes, refuse-derived fuels (RDF), and biomass fractions such as food waste, paper, plastics, sawdust, and agricultural residues. Data were extracted and synthesized based on parameters like moisture content (MC), ash content (AC), volatile matter (VM), fixed carbon (FC), higher heating value (HHV), bulk density, and flue gas emissions including O₂, CO₂, CO, NOₓ, and hydrocarbons (HC). Results and Discussion: Results indicated considerable variability in feed-stock properties: MC ranged from 0.48% to 44.30%, AC from 0.4% to 42.6%, and HHV from 13.69 to 24.30 MJ/kg, with higher energy values observed in processed and plastic-rich mixtures. Bulk density spanned 170–1200 kg/m³, favoring densified forms for improved energy storage and handling. Emission data showed wide variation—O₂ (0–45.6%), CO₂ (0–23.97%), CO (0.001–2.55%), NOₓ (0.75–5000 ppm), and HC (up to 52.9 ppm)—with elevated levels often linked to plastic and organic content. Research Implications: The findings emphasize the need for standardized feed-stock preparation, blending strategies, and emission control technologies to ensure consistent fuel quality and environmental compliance. These measures are vital for integrating MSW-based solid bio-fuels into mainstream energy systems. Originality/Value: This review offers a comprehensive synthesis of existing data on MSW-derived solid bio-fuels, combining insights on fuel quality and emission behavior. It contributes to the body of knowledge by identifying practical pathways to optimize the performance and sustainability of MSW-based energy solutions.