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A class of ruthenium-nickel alloy catalysts featured with nanoporous nanowires (NPNWs) were synthesized by a strategy combining rapid solidification with two-step dealloying. RuNi NPNWs exhibit excellent electrocatalytic activity and stability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in which the RuNi-2500 NPNWs catalyst shows an OER overpotential of 327 mV to deliver a current density of 10 mA cm−2 and the RuNi-0 NPNWs catalyst requires the overpotential of 69 mV at 10 mA cm−2 showing the best HER activity in alkaline media. Moreover, the RuNi-1500 NPNWs catalyst was used as the bifunctional electrocatalyst in a two-electrode alkaline electrolyzer for water splitting, which exhibits a low cell voltage of 1.553 V and a long-term stability of 24 h at 10 mA cm−2, demonstrating that the RuNi NPNWs catalysts can be considered as promising bifunctional alkaline electrocatalysts. A class of ruthenium-nickel alloy catalysts featured with nanoporous nanowires (NPNWs) was synthesized by a strategy combined rapid solidification with two-step dealloying, in which the total cell voltage of RuNi-1500 NPNWs electrolyzer for water splitting is 1.553 V to deliver a current density of 10 mA cm−2. [Display omitted] • A two-step dealloying strategy was used to prepare RuNi catalysts. • RuNi catalysts exhibit a unique nanoporous nanowires (NPNWs) morphology. • RuNi NPNWs catalysts show excellent electrocatalytic performance for OER and HER. • RuNi NPNWs catalysts can be used as bifunctional catalysts for water splitting. [ABSTRACT FROM AUTHOR]