The aim of the present study is to report an alternative technique of creating nickel oxide (NiO) nanofibers, manufactured by facile and economical electrospinning process. The crystallinity nature of NiO nanofibers is investigated by X-ray diffraction (XRD). Nanofibers morphology is examined by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The diameter of the nanofibers is varying from of 100–150 nm. Furthermore, Selected Area Electron Diffraction (SAED) pattern revealed that NiO nanofibers are exhibiting a single phase crystalline structure. The NiO nanofibers modified glassy carbon electrode (GCE) showed an excellent performance towards the electrocatalytic oxidation of hydrogen peroxide (H2O2). This sensor showed a wide range of detection from 10 μM to 50 mM, low limit of detection 0.33 μM and high sensitivity 42.09 μA μM−1cm−2 for H2O2 detection. The entire analysis reaffirms the suitability of NiO nanofibers as one of the futuristic sensing material for H2O2 detection. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim