In this study, the spinnability of styrene-ethyl acrylate copolymers prepared via emulsion polymerization was explored with the aim to establish the influence of glass transition temperature and polymer composition on morphological features of electrospun materials with regard to their hydrophobic/hydrophilic nature. Nonwoven mats from polymer solutions in N,N-dimethylformamide were spun using the electrospinning method (Nanospider device). It was demonstrated that changing the copolymer polarity and glass transition temperature by copolymer composition or utilizing different supporting materials might lead to nanofiber webs with controlled hydrophobic/hydrophilic properties, which predetermines them for a wide range of applications such as protective textiles, composites, etc.