Against the backdrop of escalating environmental pressure and the progressive exhaustion of fossil resources, the exploratcion of alternative energy pathways has become an increasingly pressing priority worldwide. Refuse-derived fuel (RDF), produced through dedicated pre-treatment steps that lower its moisture content and enhance its heating value, has emerged as a promising and comparatively clean substitute for conventional fuels. With the aim of advancing a more sustainable mode of energy conversion while simultaneously mitigating carbon dioxide release and safeguarding the global ecosystem, this study examined the use of CaO-bearing natural minerals — namely dolomite, limestone, and marble — as in-situ sorbents for CO2 uptake during RDF pyrolysis, in order to assess the extent to which such materials can suppress carbon dioxide emissions throughout the thermal conversion process. Thermogravimetric (TG) experiments on RDF were performed at a heating rate of 10 °C·min-1, and the resulting profiles indicated that the principal thermal degradation of RDF occurs in the temperature window between 225 °C and 600 °C. Based on the TG curves, the kinetic and thermodynamic behavior of the decomposition was subsequently evaluated and combined with Fourier transform infrared (FTIR) spectroscopy in order to obtain a more comprehensive understanding of the pyrolytic conversion of RDF. The TG–FTIR data revealed that the dominant gaseous products evolved during RDF pyrolysis consist of CO2, CH4, CO, and water vapor. Pyrolysis experiments were conducted in a fixed-bed reactor system with CO2 capture at 600°C. When dolomite is used as a trapping agent, the amount of CO2 produced is reduced from 29.34% to 14.24%. The findings of this work suggest that integrating RDF pyrolysis with mineral-based in-situ CO2 capture constitutes a highly promising route within the field of sustainable energy utilization.