We report the influence of morphological changes on the process of charge storage for electrode materials based on TiO₂ nanotubes and provide theoretical insights into the electronic properties from density-functional theory (DFT) simulations. TiO₂ nanotubes are synthesized hydrothermally from nanoparticle precursors. Structural characterization analysis reveals excellent phase purity from the XRD peaks and the formation of uniform and homogeneous nanotubes from field-emission SEM images. Interestingly, cyclic voltammetry and charge-discharge measurements demonstrate that these structurally engineered TiO₂ nanotubes exhibit an enhanced specific capacitance of about 1400 F g^-1 compared with 400 F g^-1 for pristine TiO₂ nanoparticles. Employing DFT simulations, we present the electronic and structural properties of the TiO₂ electrode for charge-storage performance. We compute the diffusion barrier of K⁺ ions in the electrolyte (KOH), the accumulated voltage for different K⁺ concentrations, and the quantum capacitance of the TiO₂ surface. A lower diffusion barrier for K+ ions and higher accumulated voltage contribute towards a superior charge-storage performance, which supports experimental observations. Hence, detailed experimental and theoretical analyses predict that a larger surface area in the tubular structure, increased number of delocalized carriers, improved conductivity, and enhanced mobility of the electrolytic ions contribute towards a fast and highly reversible electron-transfer process, leading to enhanced charge-storage performance in morphologically engineered TiO₂ nanotube-based electrodes.