Functionalization imparting zwitterionic sulfobetaines has been proven as the most versatile method for improving the hemocompatibility of polymers. In this study, we aimed to enhance the hemocompatibility of electrospun poly(ethylene‐co‐vinyl alcohol) (EVAL) by photografting with a betaine N‐(3‐sulfopropyl)‐N‐methacroyloxyethyl‐N,N‐dimethyl ammonium betaine (SMDB). SMDB was UV‐photografted to electrospun EVAL fibroporous membranes to obtain EVAL‐g‐PSMDB poly[N‐(3‐sulfopropyl)‐N‐methacroyloxyethyl‐N,N‐ dimethylammonium betaine] grafted on EVAL with different extents of grafting. The functionalization was confirmed by analysis of the attenuated total reflectance–Fourier transform infrared spectra. The effects of functionalization on the morphology, wettability, mechanical properties, and hemocompatibility of the electrospun EVAL membranes were also studied by scanning electron microscopy, water contact angle measurement, universal testing machine measurement, and in vitro hemocompatibility evaluation, respectively. The findings highlight that SMDB functionalization significantly reduced protein adsorption, hemolysis, and platelet adhesion. Blood cell consumption studies projected that the SMDB‐functionalized EVAL was able to capture leukocytes from blood, and hence, this system has the potential to be used as a filter medium for the selective removal of leukocytes from blood. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47057.