Various solvents such as ionic liquids, deep eutectic solvents, and aqueous two-phase systems have been proposed as more environmentally friendly alternatives to existing extraction processes. We suggest adding macroscopic complex coacervates to this list. Complex coacervates are liquid-like forms of polyion condensates and consist of a complex of oppositely charged polyions and water. Previous research on the biological importance of these polyion-rich phases has shown that polyion condensates have the ability to extract certain dissolved substances from water and to extract them again by changing parameters such as ionic strength and pH value. In this study, we present partition coefficients of five commonly used industrial chemicals, namely lactic acid, butanol, and three types of lipase enzymes in poly (ethyleneimine) / poly (acrylic acid) complex coacervates. It was found that the distribution coefficients can vary greatly when adjustable parameters such as polyion ratio, ionic strength, polyion and compound concentrations and temperature are varied. The distribution ratios ranged from approximately 2 to 50, depending on the tuning of the system parameters. It has also been shown that temperature swing extraction is possible, with the back-extraction of butanol from complex coacervates with a recovery of 21.1% demonstrating their potential as an extraction medium.