ZnMn2O4 has application potential in lithium ion batteries, supercapacitors, sensors, and thermistors. In this study, mesoporous spinel ZnMn2O4 nanofibers were synthesized by sol-gel assisted electrospinning combined with calcination, using poly(styrene-co-acrylonitrile) as sacrificial polymeric binder. Structural, morphological and optical properties of these ceramic nanofibers were characterized. X-ray diffraction and X-ray photoelectron spectroscopy results revealed the presence of hexagonal ZnMnO3 and MnO phases in the ZnMn2O4 nanofibers produced. Based on these observations we propose a plausible mechanism of formation of ZnMn2O4 nanofibers. The nanofibers calcined at 773 K exhibit a specific surface area of 79.5 m(2) g(-1), which is higher than that of the zinc manganite nanofibers synthesized hitherto by sol-gel electrospinning. Moreover, this material exhibits four bandgaps, which is believed to be the first observation in ZnMn2O4 nanofibers.