A series of self-supported electrocatalysts composed of tri-metallic CoFeV-LDHs generated on conductive carbon cloth (denoted as [email protected]) have been constructed. The specific interaction among Co, Fe and V is systematically revealed via tuning the molar ratios of M2+:M3+ and Fe3+:V3+ in these tri-metallic LDHs. Finally, the optimal synergistic effect is reached when the molar ratios of M2+:M3+ and Fe3+:V3+ are respectively 4:1 and 1:1, resulting in the product named Co8[email protected], which displays the best overall OER and HER performance. Only rather low overpotentials of 235 and 182 mV are required to attain the current density of 100 mA cm−2 with a Faradaic efficiency of nearly 100 % for OER and HER, respectively. Co8[email protected] can thus be applied as both an anode and cathode in the symmetrical two-electrode and possesses a current density of 100 mA cm−2 at the cell voltage of 1.65 V, and further demonstrates ultra-high stability for 100 h.