Less brittle nanofibers with excellent stability against water can be prepared via electrospinning of dispersions of styrene-acrylate copolymers from an aqueous environment. The versatility of emulsion polymerization technique allows us to tailor a wide range of properties of the dispersed polymer and the subsequent nanofibers. It was shown that the minimum film formation temperature (MFFT) and correspondingly the glass transition temperature (T-g) of the colloidal polymer, which can be varied by changing the composition of the monomers,have to be in the range of processing temperature, resulting in formation of the fibers with homogeneous morphology and good dimensional stability.