Butanol was produced from pretreated deoiled rice bran (DRB) in a batch culture of Clostridium acetobutylicum YM1. The DRB was pretreated by acetyl chloride to produce fermentable sugars prior to butanol fermentation. Pretreatment of DRB using 1% acetyl chloride (AC-DRB) resulted in sufficient fermentable sugars (30.88 g/L), which was comparable to that produced by using 1% sulfuric acid (33.5 g/L). Pretreated AC-DRB contained 18.08 g/L glucose, 9.95 g/L xylose, and 2.86 g/L cellobiose. Detoxification of AC-DRB was performed to remove the fermentation inhibitors, such as furfural, 5-hydroxymethyl furfural (HMF), acetic acid, formic acid, and levulinic acid with the removal efficiencies of 92.98%, 98.82%, 51.53%, 38.72%, and 96.21%, respectively, using charcoal. The detoxification with charcoal was more efficient compared to that with XAD-4 resin. Acetone-butanol-ethanol (ABE) fermentation of detoxified AC-DRB (with 1% AC) by XAD-4 produced 5.64 g/L butanol, while detoxification with charcoal of AC-DRB (with 1% AC) produced 6.48 g/L butanol. In detoxified AC-DRB with charcoal, the maximum butanol and ABE yield of 6.48 g/L and 11.82 g/L, respectively, were achieved. This study is the first reported treatment of biomass using acetyl chloride, which was used as a pretreatment method for successful butanol production.