Nowadays, silk fibroin receives a lot of attention as novel natural biomaterials due to its excellent biocompatibility and biodegradability. Electrohydrodynamic spraying (EHDS) is one of the method for the preparation of micro or nanoparticles by applying high voltage to the polymer solution. In this research, we fabricated silk fibroin porous microparticles by electrohydrodynamic spraying. Poly(ethylene glycol) (PEG) was added to the fibroin solution to give pores to silk fibroin microparticles. By the addition of PEG, the microparticle size was decreased despite of the decrease in conductivity and the increase of viscosity of the spraying solution. It seems that the immiscibility of silk fibroin and PEG affected much more to the microparticle size than the conductivity and viscosity. Immersing the as-sprayed microparticles into the water removed the phase-separated PEG, and finally, porous silk fibroin microparticles were prepared. The porous silk fibroin microparticles are expected to be applied as drug carriers in drug delivery or cell carriers in tissue engineering.