In this paper, we report a simple one step method of electrospraying technology to fabricate porous shell and hollow core polyurethane (PU) microspheres with uniform size. The influence of experiment conditions and solution properties such as flow rate, applied voltage, solution concentration and organic solvent on the particle size and morphology of PU microspheres were investigated. The PU polymer was prepared using 4, 4’-diphenylmethane diisocyanate (MDI) as the isocyanate, Polycaprolactone diol (PCL4000) as the diol, and 1, 4-butanediol as the chain-extending agent.Porous and solid surface morphology microspheres with sizes from several to dozens of micrometers were obtained. Results show that, PU microspheres with a diameter ranging from 2 to 30 μm were prepared by adjusting the electrospraying parameters and solution concentration. The choice of the solvent and collecting bath has a great influence on the regularities of particles. Under some appropriate conditions, we can obtain the porous-hollow polyurethane microspheres. The formation mechanism of porous-hollow morphology is contributed to the solvent evaporation with polyurethane matrix deposition and the anti-solvent induced phase separation in the water bath. The results demonstrate that the electrospraying method is a novel simple method for preparing polymer microspheres with porous surface and hollow internal structure.