Developing bifunctional electrocatalysts with features of wide source, low price and high efficiency for overall water splitting has the extremely vital significance on the energy front. Herein, we have designed and fabricated urchin-like peapoded NiCo2O4@C architecture for the first time, playing a prominent role in bifunctional alkaline catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1 M NaOH ascribed to outstanding catalytic performance and good stability. When the urchin-like peapoded NiCo2O4@C electrodes are integrated into the two-electrode system for alkaline overall water splitting, the potential as small as 1.608 V is a requisite for the current density of 10 mA cm(-2). Given high activity and long-term stability, the harvested urchin-like peapoded NiCo2O4@C is of great potential for practical application.