The fabrication capability of zirconium carbide (ZrC) nanofibers by a novel polymeric solution was examined using electrospinning method. The electrospinnable solution was prepared from the reaction of zirconium n‐propoxide (Zr(OPr)4) with acetylacetone and acetic acid followed by the addition of polyvinylpyrrolidone (PVP) solution. By utilizing thermal and microstructural analyses such as differential scanning calorimetry–thermogravimetry (DSC–TG), field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), and Brunauer–Emmett–Teller (BET), the effect of heat treatment type on the morphology and crystallinity of as‐spun PVP/Zr(OPr)4 hybrid fibers was examined. The results showed that direct carbonization treatment of as‐spun fibers under argon atmosphere led to spherical ZrC aggregates in lack of fibrillar morphology, whereas carbonization coupled with cyclization could be recognized as the unique template to govern the morphology and crystallinity of ZrC nanofibers. Carbonization of the cyclized fibers at 1550°C in flowing argon atmosphere produced the thick, fragmented rosary‐like fibers with a diameter of 357 nm, while through a 100°C decrease in carbonization temperature to 1450°C, the thin, smooth, long, and uniform ZrC nanofibers with 176 nm diameter and a medium surface area of 23 m2/g were obtained.