Pretreatment of waste emulsions with high organic content by a combined process of vibratory shear enhanced process and Fenton’s oxidation prior to biological treatment was investigated. Vibrating membrane had shown good performance in chemical oxygen demand and oil removals and the mitigation of concentration polarization. However, the permeate after filtration processing still contained high content of organics. Thus, additional Fenton oxidation was applied to reduce the organic loading, and improve the biodegradability of the wastewater. The optimal molar ratio of ferrous iron to hydrogen peroxide was 0.05 obtained from the jar-test experiments. Removal of organics was enhanced by increasing hydrogen peroxide dosage, while efficiency of hydrogen peroxide reached maximum of 1.11(w/w) at the hydrogen peroxide dosage of 6.8 g/L. Furthermore, the biological experiments indicated that the high concentration of organics could inhibit microbial activity, which decreased the chemical oxygen demand degradation rates. The adaptive period of the microbe was greatly shortened using Fenton’s reagent at the low dosages. The improvement of the biodegradability could be explained by partial mineralization and chemical transformation of parent organic compounds after Fenton oxidation.