Poly(vinyl alcohol) (PVA)/zirconium oxide (ZrO2) composite nanofibers with a skin-core structure were prepared and the effect of ZrO2 particle content on uniform web formation was investigated. The optimized polymer concentration, tip to collector distance, and applied voltage for electrospinning were 11 wt%, 12 cm, and 20 kV, respectively. Skin-core PVA/ZrO2 composite nanofibers containing up to 12 wt% ZrO2 were successfully prepared, but it was difficult to obtain PVA/ZrO2 composite nanofiber webs via conventional electrospinning. Increasing the amount of ZrO2 caused the morphology of the PVA/ZrO, composite nanofibers to become a non-uniform nanoweb with irregular nanofiber diameters. While it was difficult to obtain a uniform nanofiber web containing a content of ZrO2 over 6 wt% for conventional electrospinning, a more uniform nanofiber web could be obtained at up to 9 wt% ZrO2 using a skin-core dual nozzle. More uniform webs could also be obtained when ZrO2 was in the skin rather than the core.