In situ polymerization of poly (vinylidene fluoride) (PVDF) with hydroxyethylmethacrylate (HEMA) followed by electrospinning was employed to prepare electrospun nanofibrous membranes (ENMs), referred to as PVDF-PHEMA-ENMs. Enhanced hydrophilicity of the ENMs was observed after polymerization. A decrease in the fiber thickness resulted in a decrease in the pore size and 60% improvement in the flux. The fiber mat exhibited excellent microfiltration behavior after being coated with a surface-charged chitosan (CS) polymer, compared with its non-coated counterparts. Porosity, flux and protein adsorption studies were performed for these ENMs. A comparatively less reduced flux and better recovery ratio were observed for the PVDF-PHEMA-ENMs and CS-coated PVDF-PHEMA-ENMs due to hydrophilic pendant hydroxyl groups (from PHEMA) and/or CS groups, which can prohibit irreversible protein adsorption, on the ENM surfaces.