A generalized approach to attain spinnability in polymer solutions in electrospinning using emulsions is described. By using emulsions, low-molecular weight (MW) polymer solutions that tend to electrospray can be spun into nanofibers. Additionally, control over fiber properties independent of polymer solution viscosity and MW is achieved, with an order of magnitude reduction in fiber diameter upon emulsification. Nanofibrous sheets obtained demonstrate excellent cellular biocompatibility and are suitable for tissue contacting applications.