In this study, ruthenium-doped CoFe-based layered double hydroxides on Ni foam (CoFe-ZLDH/Ru@NF) were fabricated via an etching-precipitation strategy. The resultant CoFe-ZLDH/Ru@NF exhibited excellent activity, showing low overpotentials of 219.8 mV and 60.9 mV to reach the current density of 10 mA cm−2 for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. As a bifunctional electrocatalyst, it was assembled in an anion exchange membrane water electrolyser (AEMWE) unit, performing as an anode and cathode simultaneously, which only required a cell voltage of 2.33 V to accomplish the industrial level current density of 1 A cm−2 and operated steadily for over 12 h, making it promising for utilization in hydrogen production.