Nickel ferrite fiber (NFO–F) was synthesized using the electrospinning technique and annealed at five different temperatures (500, 600, 700, 800, and 900 °C) to study its effect on crystal structure and magnetic properties. The X-Ray diffraction pattern analysis was carried out to explore its crystal structure. The morphology and microstructure of fibers were studied by employing the Field Emission Scanning Electron Microscopy technique. The crystallinity of the material increases with the increase of annealing temperature from 500 to 900 °C. The saturation magnetization of nickel ferrite fiber increases from 31.1 to 54.0 emu/g with the increase in annealing temperature. The anisotropy constant for NFO–F calculated using the Law of Approach to Saturation (LA) and it shows the highest value for 900 °C annealed sample. Hence, the hyperthermia property of NFO–NF annealed at 900 °C has been explored. The Specific Absorption Rate (SAR) of NFO–NF calculated using Linear Response Theory and the Box-Lucas models.