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Establishing efficient nano-porous electrocatalysts for facilitating electron transfer is a one of the useful ways for enhance water splitting. Herein, Ni-Fe-Cu-Co-W high entropy alloy (NFCCW-HEA) electrocatalysts on the iron sheet substrate have been successfully prepared by a simple and efficient one-step electrodeposition method. High entropy alloys have a variety of active sites and unique atomic scale synergies, which makes the catalyst have good catalytic performance and stability. Meanwhile, the HEA coating like cauliflower by electrodeposition can provide more attachment sites, and significantly upgrade the OER catalytic activity. NFCCW-HEA catalysts exhibit an excellent overpotential of 247.3 mV under the current density of 10 mA·cm−2, and a low Tafel slope of 62.9 mV dec−1. The electrocatalyst shows long term stability of electrolysis for over 24 h in 1 mol·L−1 KOH alkaline solution, which shows good stability. We expect to provide a new idea for the preparation of nano porous high entropy alloy electrocatalysts by one-step electrodeposition technology. [Display omitted] • The nano-porous Ni-Fe-Cu-Co-W high entropy alloy electrocatalysts are prepared by a simple and efficient one-step electrodeposition method. • The formation mechanism of catalysts is carefully studied. • The unique cauliflower like nano-sheets can significantly improve the OER catalytic performance. • The synergy of multiple components • Explore different active sites [ABSTRACT FROM AUTHOR]