An efficient, rapid ex-situ detoxification has been developed to reduce inhibitor concentration and enhance acetone-butanol-ethanol (ABE) production from brewery industry liquid waste (BLW) and brewery spent grain (BSG). About 80±2.0% extraction of furan derivative and more than 95±2.0% extraction of phenolic compounds and almost no extraction of reducing sugar from simulated synthetic media as well as real waste hydrolysate have been obtained. Ex-situ extraction of microbial inhibitors from BLW and BSG hydrolysates using bis-(2-ethylhexyl) sebacate as solvent leads to high production of ABE of 12.67 g/L and 11.23 g/L respectively. Lower power consumption (0.081 W/L) and reuse of the extracting solvent made this detoxification technique extremely useful for improving production of bio-butanol from agro-industrial waste.