Pre-pulping extraction is a means of deriving a hemicellulose-rich process stream from the front end of a kraft pulp mill. When the extraction is carried out using green liquor, pulp quality and quantity can be retained while still releasing hemicelluloses and acetic acid (HAc) for recovery as bioprocessing feedstock or chemical products. The HAc that is present in the wood extraction is inhibitory to microorganisms and can hinder fermentation. HAc is also a commodity chemical that may provide sufficient value to justify recovery and purification. In this study, a liquid-liquid extraction (LLE) method is applied to extract HAc from a green liquor pre-pulping hardwood extract (GLE). The HAc removal is carried out after acid hydrolysis and prior to fermentation. Two organic solutions: trioctylphosphine oxide (TOPO) diluted in undecane and trioctylamine (TOA) diluted in octanol were tested for their abilities to extract HAc from GLE and to be recycled back through the process. GLE was contacted with the organic solvents, phase separated by centrifugation, and the organic phase was then distilled to recover the acetic acid. The solvent was then recycled back for a subsequent extraction of fresh GLE. It was found that TOA was a superior extractant, but failed to easily release its HAc through distillation. It also quickly became contaminated with other compounds in the wood extracts and lost its extraction efficiency after only a few recycles. The TOPO solvent did release its HAc through distillation but also lost extraction capacity with recycling. Back extraction of the TOPO solvent with sodium hydroxide solution restored the performance of the TOPO solvent.