Ni-based metallic foams possessing large specific surfaces and open cell structures are of specific interest as catalysts or catalyst carriers for electrolysis of water. Traditional fabrication of Nickel foam limits the element modification choices to several inert transition metals only on polymer foam precursor and subsequent preparation of foam-based catalysts in aqueous solution or organic electrolyte. To expand the modification horizon, molten salt with wide electrochemical window and fast ion diffusion can achieve the reduction of highly active elements. Herein, we reported is a general and facile method to deposit directly of highly reactive element La and prepare hierarchical honeycomb LaNi5 alloy on Ni foam (ho-LaNi5/NF). This self-supporting electrode presents excellent electrical coupling and conductivity between the Ni foam and LaNi5, which provides a 3D self-supported heterostructure with outstanding electrocatalytic activity and excellent durability for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). It exhibits excellent overpotential (1.86 V) comparable to commercial coupled IrO2//Pt/C (1.85 V) at a high current density of 100 mA cm−2. This work may pave the way for fabricating novel 3D self-supported honeycomb alloy that can be applied as electrode for usage of clean energy.