Refuse-derived fuel (RDF), a high-caloric material, is used by various combustion processes, such as power plants, as alternative fuel. Several explosion accidents, however, possibly initiated by the spontaneous combustion of stored RDF, have been reported in Japan. Therefore the spontaneous combustion of RDF prepared from domestic garbage was investigated using chemiluminescence. RDF samples were heated either under air or under nitrogen for 1, 2, or 4 h at 120 or 140 C and then cooled by an air or nitrogen stream. All RDF samples exhibited chemiluminescence. In air-treated RDF samples (heated and cooled by air), chemiluminescence after ageing was shown to be slightly lower than before ageing, whereas in nitrogen-treated samples (both heated and cooled by nitrogen) chemiluminescence decreased significantly after ageing. When nitrogen was replaced with air during aging, however, a sudden increase of chemiluminescence was observed. On the other hand, when cooling was done with air, chemiluminescence increased. Higher chemiluminescence was also observed during high-temperature treatment. Further experiments on cellulose, one of the major components of domestic garbage, exhibited similar chemiluminescence patterns to those of RDF when treated by the same methods as those used for RDF ageing. Chemiluminescence from cellulose increased significantly when the atmospheric gas was changed from nitrogen to air, suggesting that oxygen in the air promoted the formation of hydroperoxide from cellulose. Therefore, it is hypothesized that cellulose plays an important role in the formation of chemiluminescence from RDF. The formation of chemiluminescence indicated that radicals are formed from RDF by oxidation or thermal degradation at room or atmospheric temperatures and may subsequently lead to spontaneous combustion.