Copolymers of MMA, BA, and MABP are prepared by radical emulsion polymerization in water. As a result aqueous dispersions of these copolymers are obtained with particle sizes around 60120?nm. After addition of some PVA the dispersions are electrospun. The resulting fibers display different morphologies depending on the copolymer composition. Inter- and intra-particle cross-linking is achieved by photo-cross-linking induced by the MABP moieties yielding fibers with good thermomechanical properties depending on the content of MABP. With this approach, thermomechanically stable electrospun fibers with smooth surface structure can be obtained by electrospinning from water.