Poly(ethylene terephthalate)-(PET-) braid-reinforced poly(vinylidene fluoride)/graphene (PBR PVDF/GE) hollow-fiber membranes were prepared by a dry wet spinning process; they consisted of an outer-coated PVDF/GE separation layer and inner PET hollow tubular braids. GE was employed to increase the hydrophobicity of the membranes. The influences of the GE concentration in the casting solution on the structure and performance of the PBR PVDF/GE hollow-fiber membranes were investigated in terms of the pore size distribution, water contact angle (CA), water entry pressure (WEP), and differential scanning calorimetry (DSC), and the morphologies of the membranes were observed by field-emission scanning electron microscopy (FESEM). The results indicated that the as-prepared membranes completely repelled water during an 8-h continuous oil/water separation process and were hydrophobic and had a high WEP. The PBR PVDF/GE hollow-fiber membrane with 0.5 wt % GE exhibited the optimal performance and was used for reusability testing in oil/water separation. The separation efficiency of the membrane did not deteriorate with increasing number of cycles, showing an outstanding durability and reusability.