Liquid-liquid extraction (LLE) can be used for the recovery of acetic acid from black liquor prior to bioethanol fermentation. Recovery of value-added chemicals such as acetic-, formic- and lactic acid using LLE from Kraft black liquor was studied. Acetic acid and formic acid have been reported to be strong inhibitors in fermentation. The study elucidates the effect of three reaction parameters: pH (0.5~3.5), temperature (25~65 °C), and reaction time (24~48 min). Extraction performance using tri-n-octylphosphine oxide as the extractant was evaluated. The maximum acetic acid concentration achieved from hydrolyzates was 69.87% at 25°C, pH= 0.5, and 36 min. Factorial design was used to study the effects of pH, temperature, and reaction time on the maximum inhibitor extraction yield after LLE. The maximum potential extraction yield of acetic acid was 70.4% at 25.8°C, pH=0.6 and 37.2 min residence time.