Nowadays, the state-of-the-art electrocatalysts for hydrogen evolution reaction (HER) are platinum group metals. Nonetheless, Pt-based catalysts show decreased HER activity in alkaline media compared with that in acidic media due to the sluggish dissociation process of H O on the surface of Pt. With a cost 1/25 that of Pt, Ru demonstrates a favorable dissociation kinetics of absorbed H O. Herein, crystalline Ru Se nanoparticles are decorated onto TiO nanotube arrays (TNAs) to fabricate Ru Se @ TNA hybrid for HER. Owing to the large-specific surface area, Ru Se nanoparticles are freely distributed and the particle aggregation is eliminated, providing more active sites. The contracted electron transport pathway rendered by TiO nanotubes and the synergistic effect at the interface significantly improve the charge transfer efficiency in the hybrid catalyst. Compared with Ru Se nanoparticles deposited directly on the Ti foil (Ru Se/Ti) or carbon cloth (Ru Se/CC), Ru Se @ TNA shows an enhanced catalytic activity with an overpotential of 57 mV to afford a current density of 10 mA cm , a Tafel slope of 50.0 mV dec . Furthermore, the hybrid catalyst also exhibits an outstanding catalytic stability. The strategy here opens up a new synthetic avenue to the design of highly efficient hybrid electrocatalysts for hydrogen production.