Promoting efficiency of liquid–liquid extraction at a high pH is a main challenge for the recovery of volatile fatty acids (VFAs) from organic wastes. In this study, the extraction efficiency of VFAs from artificial solution and acidification fermentation broth of kitchen wastes using ionic liquids (ILs) was assessed at high pH. The effect of ILs addition ratio in diluent, volumetric solvent to feed ratio (S/F) on extraction efficiency were investigated. The solvent consists of [P666,14][Cl] (IL101) and dodecane was found to be the promising solvent for VFA extraction at pH 6.0, especially for butyric acid. The IL-101 ratio in dodecane and S/F was significant factors for the liquid–liquid extraction of VFAs. In general, a higher IL-101 ratio and S/F can promote the extraction efficiency of single VFAs. As a result, the maximum extraction rate of acetic acid (38.4–49.9%) and butyric acid (66.0–92.1%) from different VFA concentration solutions was observed at 10% IL-101 in dodecane and S/F = 2/1. The solvent was also effective in different types of real fermentation broth of kitchen wastes. The maximum extraction rate and selectivity of butyric acid was 60.2%/70.5% in butyric acid type broth and 74.6%/62.7% in mixture acid type broth.