This work aims to develop an extraction process for valuable chemicals such as phenolic bio-oil derived from pyrolysis techniques consists of a complex mixture of phenolic, organic acids, ketones and aldehydes compounds. Chemicals such as phenolic compound and acetic acid are attractive for extraction due to their high value compared to fuel and energy product. In this study, synthetic bio-oil is synthesized to represent the actual pyrolysis oil and selection of suitable salt concentrations has been investigated for systematic extraction system development. Synthetic bio-oil was characterized and the results found to be comparable with the properties of pyrolysis oil. Optimum ammonium sulfate concentration for extraction were in the range of less than 20 wt.. The highest acetic acid yields was 0.1948 wt. at 20 wt. concentration of (NH 4)2SO4. While, phenol was rich in organic phase with the highest yield at 30 wt. of (NH4)2SO 4. Copyright © 2014 Trans Tech Publications Ltd, Switzerland.