Abstract Complexation extraction with trioctylamine (TOA) as solvent for the recovery of acetic acid from bio-oil was studied. The effects of TOA concentration, iso-octyl alcohol concentration, volume ratio of extractant/distillate and temperature on extraction efficiency were examined. Experimental results indicated that the extraction efficiency was the highest with 40% TOA+40% iso-octyl alcohol+20% kerosene and 3∶1 volume ratio of extractant/distillate at the temperature of 0 ℃. And an extraction efficiency of 74.6% for acetic acid was achieved in a single-equilibrium-stage extraction under this optimal condition.