Layered double hydroxides have been widely applied for oxygen evolution reaction (OER) in the alkaline water electrolysis. However, the issues of poor connection between the catalyst and nickel foam and the specific mechanisms for active sites has not been fully documented. In this study, the in-situ nickel foam etching in a mixed solution of ferric chloride and cobalt nitrate at low temperatures was adopted for NiCoFe layered ternary hydroxides (NiCoFe LTHs) synthesis with a better tight integration. Physicochemical characterization indicated that the NiCoFe LTHs could grow directly through corroding nickel foam with a nano-flower-like morphology and structures. That is favorable for electron transfer from the catalytic layer to the conductive substrate. With the transition metal ions interaction and the tight integration construction, NiCo1Fe4-LTH-T60/NF presented an enhanced electrolysis performance with the overpotential of 234 mV (1.464 V vs. RHE) at current density of 100 mA cm−2 in 1 M KOH electrolyte. The Tafel slope for NiCo1Fe4-LTH-T60/NF electrode was 36.19 mV dec−1 for an enhanced OER kinetics. Besides, it demonstrated faster interfacial charge transfer process, better intrinsic electrochemical activity and stability in large current stability testing. It was revealed that the synergistic effect of the transition metal ions interaction enhancement and the mechanism of oxygen evolution elementary reaction for NiCo1Fe4-LTH-T60/NF during the water electrolysis by the electrochemical and theoretical calculation. This work provides theoretical basis and experimental support for the design and synthesis of future OER catalyst and substrate, which is significant for hydrogen and oxygen generation from water electrolysis.