Materials on the scale of nanoscale have widely been used as research topics because of their interesting characteristics and aspects they bring into the field. Out of the many metal oxides, zinc oxide (ZnO) was chosen to be fabricated as nanofibers using the electrospinning method for potential uses of solar cells and sensors. After ZnO nanofibers were obtained, calcination temperature effects on the ZnO nanofibers were studied and reported here. The results of scanning electron microscopy (SEM) revealed that the aggregation of the ZnO nanofibers progressed by calcination. X-ray diffraction (XRD) study showed the hcp ZnO structure was enhanced by calcination at 873 and 1173 K. Transmission electron microscopy (TEM) confirmed the crystallinity of the calcined ZnO nanofibers. X-ray photoelectron spectroscopy (XPS) verified the thermal oxidation of Zn species by calcination in the nanofibers. These techniques have helped us deduce the facts that the diameter of ZnO increases as the calcination temperature was raised; the process of calcination affects the crystallinity of ZnO nanofibers, and the thermal oxidation of Zn species was observed as the calcination temperature was raised.