Well-defined submicrometer structures of poly(dimethylaminoethyl methacrylate) (PDMAEMA) were grafted from 100 μm thick films of poly(ethene-alt-tetrafluoroethene) after electron-beam lithographic exposure. To explore the possibilities and limits of the method under different exposure conditions, two different acceleration voltages (2.5 and 100 keV) were employed. First, the influence of electron energy and dose on the extent of grafting and on the structure’s morphology was determined via atomic force microscopy. The surface grafting with PDMAEMA was confirmed by advanced surface analytical techniques such as time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy. Additionally, the possibility of effective postpolymerization modification of grafted structures was demonstrated by quaternization of the grafted PDMAEMA to the polycationic QPDMAEMA form and by exploiting electrostatic interactions to bind charged organic dyes and functional proteins.