Volatile fatty acids (VFAs) are produced by fermentation of various bio-sources and human wastes at minimal cost; sometimes, even sources having a prepaid processing fee were used. However, low concentrations of VFAs in water have prevented their commercial production, even with modern separation technologies, due to the high operating costs. We have applied newly developed solvents, selected by chemical structure similarity, to the separation of five different VFAs. Since most of the water was separated by extraction using hexyl acetate and nonyl acetate, the utilities necessary for solvent recovery and product purification were a fraction of those required by the existing VFAs’ separation processes. The solvents separated almost all the water in the feed at the extraction stage, consuming no energy. The energy use in this study is only 34% of the lowest case use among various processes of either distillation-only or combined extraction–distillation. The performance evaluation of the proposed VFAs separation process showed that product recovery was 99% and acid purity was 99.5% with eco-scores of 70% lower than those of the current processes.