Developing efficient, durable, and earth-abundant electrocatalysts for both hydrogen and oxygen evolution reactions is important for realizing large-scale water splitting. The authors report that FeB2 nanoparticles, prepared by a facile chemical reduction of Fe2+ using LiBH4 in an organic solvent, are a superb bifunctional electrocatalyst for overall water splitting. The FeB2 electrode delivers a current density of 10 mA cm−2 at overpotentials of 61 mV for hydrogen evolution reaction (HER) and 296 mV for oxygen evolution reaction (OER) in alkaline electrolyte with Tafel slopes of 87.5 and 52.4 mV dec−1, respectively. The electrode can sustain the HER at an overpotential of 100 mV for 24 h and OER for 1000 cyclic voltammetry cycles with negligible degradation. Density function theory calculations demonstrate that the boron-rich surface possesses appropriate binding energy for chemisorption and desorption of hydrogen-containing intermediates, thus favoring the HER process. The excellent OER activity of FeB2 is ascribed to the formation of a FeOOH/FeB2 heterojunction during water oxidation. An alkaline electrolyzer is constructed using two identical FeB2-NF electrodes as both anode and cathode, which can achieve a current density of 10 mA cm−2 at 1.57 V for overall water splitting with a faradaic efficiency of nearly 100%, rivalling the integrated state-of-the-art Pt/C and RuO2/C.