Cost-effective, efficient and stable electrocatalyst for water splitting in the acidic electrolyte medium has been developed. The acidic electrolyte could be a support for the high purity hydrogen production via water splitting. Accordingly, we have prepared the defect-rich titania nanostructure via electrochemical anodization and cathodization routes using the titanium plate, which showed highly effective and durable electrocatalyst of hydrogen evolution reaction (HER) in an acidic medium. This hybrid compound showed a low onset potential of −0.17 V for HER with a current density of −150 mA cm−2 in 1 M H2SO4. Moreover, the stability test has been performed with the defect-rich titania nanostructure as cathode for 6 h in the two electrodes system.