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• A composite with MoNi 4 alloys embedding into MoO 3-x porous nanorods was synthesized via a simple in-situ reduction method. • The obtained MoNi 4 @MoO 3-x exhibits a remarkable HER activity with 10 mA/cm2 constant current under 58.6 mV low overpotential. • The remarkable HER activity is found to originate from the MoNi 4 alloys, excellent conductivity and porous structure. [Display omitted] Hydrogen evolution reaction (HER) in alkaline media is expected to become a renewable and economical technology for hydrogen production. Various non-noble electrocatalysts have been explored for HER, in which Ni-Mo alloy is one of the best media. However, its syntheses are complicated and costly. In this work, we contribute an in-situ reduction method of porous MoNi 4 @MoO 3- x nanorods. The synthesized MoNi 4 @MoO 3- x exhibits a remarkable HER activity with 10 mA/cm2 constant current under 58.6 mV extremely low overpotential, small Tafel slope of 44.8 mV/decade, and high durability in 1 M potassium hydroxide electrolyte. Its remarkable activity is found to originate from the highly activity of MoNi 4 , excellent conductivity and favorable porous structure. This work is believed to provide a promising strategy for the HER development of highly active and cost-effective electrocatalysts. [ABSTRACT FROM AUTHOR]