A novel hydrophilic PVDF composite membrane based on ZrO2-multiwalled carbon nanotubes (MWCNTs) hybrid was prepared by a simple phase-inversion method. ZrO2 nanoparticles were firstly loaded on the surface of MWCNTs via hydrothermal route, which was characterized by Fourier-transform infrared, X-ray diffraction, thermogravimetric analyzer, scanning electron microscopy (SEM), and transmission electron microscopy. It was found that the ZrO2-MWCNTs hybrid formed network structures within the PVDF matrix, avoiding the aggregation of nanofillers. Then, the effects of ZrO2-MWCNTs hybrid on the performances of ultimate PVDF membrane were systematically investigated. The microstructure and surface morphology of novel membranes were observed by SEM and atomic force microscopy. The results indicated that ZrO2 were dispersed homogeneously on the surface of MWCNTs. The as-prepared membrane exhibited enhanced pure water flux and a lower contact angle than those of pure PVDF membrane. Furthermore, the as-prepared membranes processed also improved separation efficiency against oil/water emulsions and achieved better rejection ratio and good durable antifouling performance. In general, ZrO2-MWCNTs/PVDF membrane may provide a potential application against complex oil/water systems.