A poly(vinylidene fluoride) (PVDF) hollow fiber membrane surface was modified by alkaline treatment in this study. This subject was selected with the aim to confirm the mechanisms of alkaline degradation of PVDF membranes, characterize the variations of membrane surface morphology (e.g., average pore size, pore size distribution, porosity, etc.), and estimate the membrane fouling potential by a bench-scale test with synthetic surface water. The conditions of the alkaline treatment covered various concentrations, temperature, and processing time. The results of this study indicate that the hydrophilic PVDF membranes can be obtained after appropriate treatment without loss of integrity of the membrane surface. All factors, including the concentration of NaOH, temperature, and processing time affect membrane properties. The surface images and air flow rate of unmodified and modified membranes showed difference in their average pore size and pore size distribution. In general, the increase of the processing time decreases the average pore size at constant concentration and temperature; the increase of the NaOH concentration in solution and temperature fastens the degradation process. Membrane pure water flux decreased after alkaline treatment. This can be attributed to the decrease of pore size. However, the membrane anti-fouling potential increased after alkaline treatment due to the enhancement of hydrophilic property of membrane surface.