Distilled grain waste (DGW) eluted from the Chinese liquor making process poses potential serious environmental problems. The objective of this study is to evaluate the feasibility of converting DGW to biogas by thermophilic dry anaerobic digestion. To improve biogas production, the effects of dilute H2SO4 and thermal pretreatment on DGW were evaluated by biochemical methane potential (BMP) tests. The results indicate that 90 A degrees C thermal pretreatment provided the highest methane production at 212.7 mL/g-VTSadd. The long-term thermophilic dry anaerobic digestion process was conducted in a 5-L separable flask for more than 3 years at a volatile total solid (VTS) loading rate of 1 g/kg-sludge/d, using synthetic waste, untreated and 90 A degrees C thermal pretreated DGW as the feedstock, respectively. A higher methane production, 451.6 mL/g-VTSadd, was obtained when synthetic waste was used; the methane production decreased to 139.4 mL/g-VTSadd when the untreated DGW was used. The 90 A degrees C thermal pretreated DGW increased the methane production to 190.5 mL/g-VTSadd, showing an increase of 36.7% in methane production compared with that using untreated DGW. The microbial community structure analysis indicates that the microbial community in the thermophilic dry anaerobic digestion system maintained a similar structure when untreated or pretreated DGW was used, whereas the structure differed significantly when synthetic waste was used as the feedstock.