Nowadays, materials that possess high activity and natural oxygen vacancy have garnered significant attention as potential electrode materials for supercapacitors. In this study, we successfully prepared the Hf6Ta2O17 (HTO) nanofibres (NFs) with an orthorhombic superlattice structure using the electrospinning technique and sintering process. The characterization results indicate that the HTO NFs synthesized at 750 °C show good micro nanostructures and outstanding electrochemical properties. To enhance its energy storage performance, additional oxygen vacancies (OVs) were introduced through a carbothermal treatment under an Ar atmosphere. Although longer reduction reaction times can produce more OVs, the integration of grain boundaries and the growth of grain size caused by large annealing times may limit its electrochemical performance. Therefore, the HTO NFs treated for 1 h (HTO/C-1) exhibited the maximum Cs of 925 F·g−1 at 1 A·g−1 with a larger voltage window of 2.1 V. Furthermore, a symmetric supercapacitor fabricated by two reduced HTO NFs electrodes and 1 M Na2SO4 solution, recorded as r-HTO NFs//r-HTO NFs. The device demonstrated excellent energy density of 73.3 Wh·kg−1 (at power density of 1050 W·kg−1) and a long cycling life (81.8% retained after 5000 cycles). These results suggest that the optimized reduction process can provide appropriate oxygen vacancies in HTO NFs, thereby effectively enhancing its performance.