Low-cost and highly efficient bifunctional electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are intensively investigated for overall water splitting. Herein, we combined experimental research with first-principles calculations based on density functional theory (DFT) to engineer the NiCo2S4@NiFe LDH heterostructure interface for enhancing overall water-splitting activity. The DFT calculations exhibit strong interaction and charge transfer between NiCo2S4 and NiFe LDH, which change the interfacial electronic structure and surface reactivity. The calculated chemisorption free energy of hydroxide (ΔEOH) is reduced from 1.56 eV for pure NiFe LDH to 1.03 eV for the heterostructures, indicating a dramatic improvement in OER performance, while the chemisorption free energy of hydrogen (ΔEH) maintains almost invariable. By the use of the facile hydrothermal method, NiCo2S4 nanotubes, NiFe LDH nanosheets, and NiCo2S4@NiFe LDH heterostructures are prepared on nickel foam, of which the corresponding experimental OER overpotentials are 306, 260, and 201 mV at 60 mA cm-2, respectively. These results are good agreement with the theoretical predictions. Meanwhile, the HER performance has little improvement, with an overpotential of about 200 mV at 10 mA cm-2. Due to the dramatic improvement in OER performance, there was an enhancement in the overall water-splitting activity of the NiCo2S4@NiFe LDH heterostructures, with a low voltage of 1.6 V.