A facile method, i.e., nonsolvent assisted electrospraying, is proposed to fabricate hierarchically porous microspheres. The pore size on the microsphere surface ranges from a few tens to several hundred nanometers. Thermally and nonsolvent induced phase separation as well as breath figure is responsible for the formation of the hierarchical structures with different nano-sized pores. The nonsolvent could not only induce phase separation, but also stabilize the interface between the droplet and air, which can prevent the droplet from strong deformation, and is therefore beneficial to the formation of regular and uniform microspheres. On the other hand, solvent evaporation, polymer diffusion and Coulomb fission during electrospraying influence the morphology of finally obtained products. In this paper, the influence of polymer concentration, the weight ratio between nonsolvent and polymer and the flowing rate on the morphology of the porous microsphere is carefully studied. The hierarchically porous microsphere significantly increases the surface roughness and thus the hydrophobicity, and the contact angle can reach as high as 152.2 ± 1.2°. This nonsolvent assisted electrospraying opens a new way to fabricate superhydrophobic coating materials.