Zinc oxide (ZnO) nanoparticles (NPs) anchored to carbon nanofiber (CNF) hybrids were synthesized using a facile coprecipitation method. This report demonstrates an effective strategy to intrinsically improve the conductivity and supercapacitive performance of the hybrids by inducing oxygen vacancies. Oxygen deficiency-related defect analyses were performed qualitatively as well as quantitatively using Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. All of the analyses clearly indicate an increase in oxygen deficiencies in the hybrids with an increase in the vacuum-annealing temperature. The nonstoichiometric oxygen vacancy is mainly induced via the migration of the lattice oxygen into interstitial sites at elevated temperature (300 °C), followed by diffusion into the gaseous phase with further increase in the annealing temperature (600 °C) in an oxygen-deficient atmosphere. This induction of oxygen vacancy is corroborated by diffuse reflectance spectroscopy, which depicts the oxygen-vacancy-induced bandgap narrowing of the ZnO NPs within the hybrids. At a current density of 3 A g(-1), the hybrid electrode exhibited higher energy density (119.85 Wh kg(-1)) and power density (19.225 kW kg(-1)) compared to a control ZnO electrode (48.01 Wh kg(-1) and 17.687 kW kg(-1)). The enhanced supercapacitive performance is mainly ascribed to the good interfacial contact between CNF and ZnO, high oxygen deficiency, and fewer defects in the hybrid. Our results are expected to provide new insights into improving the electrochemical properties of various composites/hybrids.