<p>Preparing cheap, stable and effective electrocatalytic for oxygen evolution catalysts is urgent. A two-step hydrothermal method was applied to synthesis the heterostructural catalyst of Ni₃S₂/NiFe-LDH/NF in this study. The experiment demonstrates that Ni₃S₂ could grow on the edges of NiFe-LDH. At 100&#xa0;mA·cm^− 2, the Ni₃S₂/NiFe-LDH/NF shows 264 mV overpotential for oxygen evolution reaction (OER) which is lower than that of NiFe-LDH/NF and Ni₃S₂/NF. The electrochemical analysis shows that the heterostructure in Ni₃S₂/NiFe-LDH/NF could increase the effective charge transfer, active sites and adjusts the adsorption-desorption energy of OER performance. Also, the Ni₃S₂/NiFe-LDH/NF showed long-term stability, which is a candidate for water electrolysis applications in practice.</p> Graphical Abstract <p></p>