Here, we report on how the energy band diagram of a nanostructured semiconductor-metal interface aligns in accordance with semiconductor morphology. Electrochemically, titanium metal is anodized to form titanium dioxide nanotubes, which forms a junction with the free Ti substrate and this junction forms a natural Schottky barrier. With reduced dimensionality of the nanotube structures (lower wall thickness), we have observed band edge movements and band gap quantum confinement effects and lowering of the Schottky barrier. These results were corroborated with the help of cyclic voltammetry, ultraviolet-visible spectrometry, and impedance analysis. Current voltage analysis of the Schottky barrier showed a lowering of the barrier (by 25 %) with reducing dimensionality of the nanotube structures. At externally applied voltages higher than the Schottky barrier, charges can travel along the nanotubes and reside at an interface between the nanotubes and a high-κ dielectric. This property was utilized to develop high surface area solid-state capacitors.