Scientists are much interested in hydrogen, which is one of the most promising energy vectors. Produced from water hydrogen after use in fuel cell or IC engine burns back to water hence it is clean, climate friendly and renewable. Solar route for hydrogen production by splitting of water with titanium dioxide nanostructures offers a renewable energy source. Aligned titanium oxide nanotubes electrodes have been synthesized by anodization of high purity Ti-sheet (Good fellow Ltd, UK) in a fluoride mediated electrolytic media at an applied potential ~20V for ~2 hrs. Structural/microstructural characterizations of TiO₂ nanotubes were done through scanning & transmission electron microscopes (SEM &TEM). SEM and TEM results shows that TiO₂ nanotubes are well aligned in the bundles with their diameter ranging ~70-100 nm and lengths ~450-600 nm and the selected area electron diffraction pattern of the TiO₂nanotube corresponds to anatase phase. Optical characterizations through UV-Visible spectroscopy revealed that the band gap of TiO₂ nanotubes is ~3.23 eV. Photoelectrochemical characterizations and hydrogen production studies of these TiO₂ electrodes revealed that nanotubes can be very effective photoanodes for photoelectrochemical water splitting for hydrogen production using solar energy. Photoelectrochemical characterization of the PEC cell with TiO₂ nanotubes in the standard three electrode configuration, with ~1.0M NaOH electrolyte and saturated calomel (SCE) reference electrode, shows the effect of light illumination (photocurrent density ~1.42 mA/cm²)as compared to the dark current density at nearly same applied potential. A hydrogen production rate upto ~6.45 lh^-1m^-2 has so far been obtained, further improvements are expected.