The discovery of black TiO2 nanospheres opens new avenues for various energy applications. In this study, a novel approach of laser annealing is used for the fabrication of black TiO2 nanospheres. Laser irradiation of TiO₂ in liquid is a promising method due to its simplicity and less usage of toxic reagents, for tailoring the bandgap of black TiO₂ for various energy applications. X-ray diffraction (XRD), Scanning electron microscope (SEM), Raman spectroscopy, UV-visible spectroscopy, Photoluminescence (PL), and FTIR spectroscopy were used to characterize the structural, morphological, optical, and defect properties of the synthesized materials. High energy (50 mJ) laser irradiation led to a phase transformation from anatase to rutile in the TiO₂ nanoparticles, as demonstrated by the strengthening of rutile peaks and the weakening of anatase peaks in the XRD spectra. The formation of Ti³⁺ species and surface disorder lead to a significant reduction in bandgap and enhanced visible light absorption in UV-visible spectroscopy. Electrochemical testing shows exceptional performance of laser modified black TiO2 nanospheres, with a specific capacitance of 3189 F/g at 1 A/g in 1 M NaOH. This work presents potential advancements in energy storage technology by elucidating the possibility of black TiO2 nanospheres as effective electrode materials for energy storage devices.