Foreign metal ions with reducing ability were doped into NiFe layered double hydroxides (NiFe-LDHs) to activate the basal plane in NiFe-LDHs for oxygen evolution reaction (OER). Mn2+-Doped NiFe-LDH array electrode yields a low onset potential of 1.41 V and exhibits outstanding stability. The study herein illustrates a new dimension of electronic structure regulation and promises further optimization of highly efficient electrocatalysts.