ZrO2 nanofibers with controllable crystalline phase were fabricated via a halide-free strategy. Polyvinylpyrrolidone(PVP)/Zr(NO3)(4), precursor nanofibers were first synthesized using electrospinning method. After sintering such precursor nanofibers at high temperature, the PVP and Zr (NO3)(4) decomposed and the resulting ZrO2 nanofibers formed. The crystal structure, morphology and thermal stability were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and thermogravimetric analysis. The morphology and crystal structure of ZrO2 nanomaterials could be tuned by controlling calcination temperature.