Electrospun atactic polypropylene (PP) fibers are thicker than those obtained from isotactic PP, although the viscosity of molten PPs is almost same. Thus we focused on the effect of tacticity of PP on fiber diameters. The PP samples with various tacticity were prepared by changing the blend ratio of isotactic PP and atactic PP. Melt-electrospinning is performed by using blended samples, and then electrospun fibers were observed by scanning electron microscope to evaluate fiber diameter of obtained fibers. It is clear that the diameter of electrospun PP fibers decreases as high tacticity content of PP increases. This result suggests that tacticity of samples is an important factor to control the electrospun fiber diameter.