Nanofiber production was investigated from poly(ethylene terephthalate) (PET) polymers functionalized with hydroxyethyl methacrylate (HEMA) by grafting of HEMA monomers onto the PET fibers. HEMA grafted PET (PET-g-HEMA) copolymers were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy. PET and PET-g-HEMA were dissolved in trifluoroacetic acid and nanofibers were obtained by electrospinning. It was found that the PET and PET-g-HEMA polymers having grafting yield 20 and 55% could be converted to continuous, smooth, and beadles nanofibers. For characterization of the nanofiber membranes, thermogravimetric analysis, differential scanning calorimeter analysis, surface contact angle measurement, porosity analysis, and mechanical tests were applied. When compared with the original PET nanofibers, the thermal properties and degradation process of PET-g-HEMA nanofibers changed according to the amount of HEMA present in the structure of nanofibers. The contact angles of the nanofibers obtained from PET-g-HEMA polymers decreased whereas the water retention ability of the nanofibers increased compared to original PET nanofibers. The porosity of PET-g-HEMA nanofibers was found be high compared to PET nanofibers and whereas the mechanical properties of PET was higher than PET-g-HEMA nanofibers. The obtained nanofibers can be used in many fields such as biomaterial applications.