Polymethylmethacrylate (PMMA) microspheres with various morphologies are fabricated by nonsolvent assisted electrospraying. The morphology evolution is determined by nonsolvent properties including the solubility parameter, surface tension and viscosity, and nonsolvent induced phase separation is the main reason for the formation of the porous and/or hollow structures. It is found that nonsolvent possessing a high surface tension is beneficial to the formation of a hollow structure, while the large phase separation tendency between nonsolvent and the polymer can promote pore generation on the sphere surface. The nanosized pores, especially hierarchical pores, can enhance the hydrophobicity of the substrate surface coated with these microspheres. On the other hand, nonsolvent with a large viscosity could prevent the growth of the phase separated nuclei, leading to the presence of relatively small and discontinuous pores on the microsphere surface, which can finally cause the decrease of the contact angles. The surface pores of the electrosprayed microspheres are even eliminated if polymer additive, i.e., PVP, is incorporated into the polymer-solvent-nonsolvent solution. The addition of PVP renders the microsphere coated surface hydrophilic, which can be completely wetted by water droplets. (C) 2014 Elsevier Ltd. All rights reserved.