Polyvinylidene fluoride (PVDF) hollow fibers were hydrophobically modified using a simple and scalable method of plasma activation and silane grafting. The effects of plasma gas, applied voltage, activation time, silane type, and concentration were investigated according to the membrane hydrophobicity and direct contact membrane distillation (DCMD) performance. Two kinds of silane were used, including methyl trichloroalkyl silane (MTCS) and 1H,1H,2H,2H-perfluorooctane trichlorosilane silanes (PTCS). The membranes were characterized by techniques such as Fourier transform infrared (FTIR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and contact angle. The contact angle of the pristine membrane was 88°, which increased to 112°-116° after modification. Meanwhile, the pore size and porosity decreased. In DCMD, the maximum rejection reached 99.95% by the MTCS-grafted membrane, while the flux decreased by 35% and 65% for the MTCS- and PTCS-grafted membranes, respectively. Treating humic acid-contained solution, the modified membrane showed steadier water flux and higher salt rejection than the pristine membrane, and 100% flux recovery was achieved by simple water flushing. This two-step method of plasma activation and silane grafting is very simple and effective to improve the hydrophobicity and DCMD performance of PVDF hollow fibers. However, further study on improving the water flux should be carried out.