ZnO nanofibers were synthesized using an electrospinning method with polyvinyl alcohol and zinc acetate as precursor materials. The effects of the processing parameters on the microstructure of the synthesized ZnO nanofibers were investigated. X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy showed that the ZnO nanofibers were distributed uniformly over the Si substrates and had a polycrystalline nature. Individual nanofibers consisted of nanograins. Interestingly, the nanograins coalesced and grew under higher calcination temperatures and longer calcination times. The activation energy for grain-growth was estimated to be 13.126 kJ/mol, and the dominant growth mechanism was most likely to be related to lattice diffusion in pore control mode.