Hybridization has evolved a powerful toolbox for hierarchical structure manipulation of antifouling membrane surface. In this study, zwitterionic and fluorine-containing moieties are immobilized onto the surface of TiO2 nanoparticles through the mediation of polydopamine, and the resultant nanoparticles are incorporated into poly(vinylidene fluoride) (PVDF) matrix to simultaneously manipulate the chemical and topological structures of membrane surfaces. The hierarchical topographies of the hybrid membranes arise from the morphology of nanoparticles. The surface heterogeneity of the hybrid membranes arises from the different chemical moieties on nanoparticles, endowing the membrane surfaces with both hydrophilic zwitterionic segments and low surface energy fluorine-containing segments. Due to the favorable hierarchical chemical and physical structures, the hybrid membranes display a remarkable enhancement in oil-fouling-resistant and oil-fouling-release capacities during oil-in-water emulsion filtration: the flux declines at the minimum level of 16.7% and recovers to the maximum level about 100%. It can be anticipated that the present study will offer a physico-chemical coordinated antifouling mechanisms to control membrane oil-fouling for the efficient oil-containing wastewater treatment.