Municipal solid waste (MSW) usually contains a considerable amount of chlorine, which is typically associated with the limited beneficial uses of these materials. In this study, the effect of chlorine on the structure and reactivity of char derived from pyrolysis of MSW materials with air at 500 degrees C were investigated. The combustion reactivity rate of six different char samples with NaCl and NaHCO3 addition was characterized with thermogravimetric analysis. The carbonization level, the crystal carbon structure, and the morphology of char samples were described by Raman spectroscopy, X-ray diffractometry, and scanning electron microscopy. Results indicated that the reactivity of char with NaCl addition was reduced compared to char samples prepared with NaHCO3, associated with the inhibiting effect of inorganic chlorine. The XRD spectra revealed that the crystal carbon structure was strengthened by the presence of sodium and weakened by the presence of inorganic chlorine. The Raman spectroscopy analysis exhibited that the reactivity of the char samples was directly proportional to the band ratio of I-D/I-G, which also confirmed that the char samples produced with NaHCO3 addition were featured with a weakened graphite structure compared to the char samples produced with NaCl addition. Also, the char samples produced with NaHCO3 addition possessed a denser microstructure, which resulted in a larger specific surface area.