The exploitation of cost-effective and abundant non-noble metal electrocatalysts holds great significances in enhancing the efficiency of oxygen evolution reaction (OER) and/or urea oxidation reaction (UOR). Herein, we report an electrocatalyst with co-existing V-dopants and Ni(OH)/FeOOH interfaces (referred to as A-NiFeV/NF, with "A" indicating "activated"). The electron coupling between Ni, Fe and V, analyzed through X-ray photoelectron spectroscopy, indicates that Ni and Fe both receive electrons from the V. Additionally, the Fe can also lead to a bias toward a lower valence of the Ni centers in Ni(OH). Further in situ Raman spectroscopy reveals that Ni(OH) inevitably undergoes transformation into amorphous NiOOH during the activation process, however, the synergistic effects of V-dopants and Ni(OH)/FeOOH interfaces keep the Ni centers mostly in a lower oxidation state of +2 even at high potential ranges. These low-valence Ni centers are proposed to be positively correlated with the optimized OER activity of the Ni-based electrocatalysts. As a result, the designed A-NiFeV/NF electrocatalyst exhibits low overpotentials of 234 and 313 mV to propel current densities of 10 and 100 mA/cm, and a small Tafel slope of 37.8 mV/dec for OER in 1.0 M KOH. The catalyst demonstrates a stable OER activity for over 100 h at 100 mA/cm. Additionally, it can be integrated with a solar cell to construct a solar-driven electrolytic OER device without additional electric input. Similarly, for the small molecule oxidation, UOR, only ∼1.33 and ∼1.39 V vs. RHE (RHE: reversible hydrogen electrode) are required to achieve 10 and 100 mA/cm, respectively, in an electrolyte composed of 1.0 M KOH with 0.33 M urea.