Here, we show a ruthenium-titanium alloy oxide (RuTiO) on a 3D web-like titania for iodide oxidation reaction (IOR) and simultaneously to boost hydrogen production by water electrolysis. The FT-EXAFS results of Ru K-edge in the RuTiO catalyst show the presence of Ru-Ti bonding in the second shell. The developed RuTiO requires an ultralow cell voltage of 1.09 V to achieve 10 mA cm^-2 for IOR-based electrolysis, whereas the Faradaic efficiency for H₂ production is almost 100 % at the cathode. The RuTiO remains stable in a 36-hours test without degradation, indicating that the electrocatalyst could be used as a robust anode in an IOR-based electrolysis for value-added H₂ production. This proves that IOR-based electrolysis is more energy-saving for value-added H₂ production when compared to water electrolysis. This finding paves a route to design other electrocatalysts on 3D web-like titania with improved catalytic activity and prolonged stability for IOR-based electrolysis.