Membranes with hierarchical architectures consisted of 1D and 2D materials have shown excellent performance in emulsified oil/water separation, but the roles of 2D layered materials in oil/water separation and anti-fouling performance are still to be clarified. Here, we used a facile layer-by-layer assembling approach to fabricate 3D hierarchical membranes using a porous cellulose acetate support membrane coated with graphene oxide ( GO) or layered double hydroxides (LDH) grafted with sepiolite (SeP), and then the roles of GO and LDH in oil/water separation and anti-fouling performances of these hierarchically modified membranes were investigated. Results of characterization experiments showed that these membranes were successfully fabricated. Wetting behavior of these membranes indicated that the hierarchical structure can provide high permeate flux and underwater superoleophobic properties. Though the fabrication processes were similar, the surface of SeP + GO and Sep + LDH coated membrane showed different morphologies. After cyclic oil/water separation experiments we found that SeP + GO coated membranes exhibited higher flux and slower decline of permeation than SeP + LDH coated membranes due to its unique properties. Our research demonstrated that the properties of 2D layered materials play important roles in determining water permeability and anti-oil-fouling performance of modified membranes with hierarchical structure.