Polyvinylidene fluoride (PVDF) fibrous membranes with fiber diameter from nanoscale to microscale were prepared by electrospinning. The structural parameters of PVDF fibrous membrane in terms of fiber diameter, pore size and its distribution, porosity or packing density, thickness, and areal weight were tested. The relationship between solution concentration and structural parameters of fibrous membrane was analyzed. The filtration performance of PVDF fibrous membrane in terms of air permeability and filtration efficiency was evaluated. The results demonstrated that the higher solution concentration led to a larger fiber diameter and higher areal weight of fibrous membrane. However, no regular change was found in thickness, porosity, or pore size of fibrous membrane under different solution concentrations. The air permeability and filtration efficiency of fibrous membrane had positive correlations with pore size. The experimental results of filtration efficiency were compared with the predicted values from current theoretical models based on single fiber filtration efficiency. However, the predicted values did not have a good agreement with experimental results since the fiber diameter was in nanoscale and the ratio of particle size to fiber diameter was much larger than the value that the theoretical model requires.