This work concentrates on the pyrolysis and char characterization of a refuse-derived fuel (RDF), produced from municipal solid waste, and five of its components, namely, nonpackaging paper, food, textile, low-density polyethylene film, LDPE, and packaging polypropylene wastes. Specifically, this work characterizes physically and chemically the materials, examines the pyrolysis and oxidation patterns of the RDF and its components using thermogravimetric analysis (TGA) and a quartz reactor (QR), respectively, evaluates the reactivity toward oxygen of selected RDF chars at 650 degrees C in the QR, and characterizes the trace organics emission during the pyrolysis and chars oxidation in the QR by means of gas chromatography coupled with mass spectrometry. The main conclusions of this study are as follows: (1) the pyrolysis and oxidation patterns indicate the presence of low-stability organic components, lignocellulosic materials, and plastics but with the maximum rates occurring at lower temperatures than those reported in the literature; (2) the reactivity toward oxygen of chars at 650 degrees C revealed that the food waste and the LDPE film waste chars are among the less reactive chars, while the textiles waste and the packaging PP waste chars are among the more reactive chars; the RDF char reactivity resembles mostly that of the nonpackaging paper waste char; (3) analyses of the trace organic elements released reflect the transversal contamination of the different materials that compose RDF, derived from its mixed origin. During both pyrolysis and char combustion, phthalates were the most relevant compounds encountered.