Abstract A highly active FeSe 2 electrocatalyst for durable overall water splitting was prepared from a molecular 2Fe‐2Se precursor. The as‐synthesized FeSe 2 was electrophoretically deposited on nickel foam and applied to the oxygen and hydrogen evolution reactions (OER and HER, respectively) in alkaline media. When used as an oxygen‐evolution electrode, a low 245 mV overpotential was achieved at a current density of 10 mA cm −2 , representing outstanding catalytic activity and stability because of Fe(OH) 2 /FeOOH active sites formed at the surface of FeSe 2 . Remarkably, the system is also favorable for the HER. Moreover, an overall water‐splitting setup was fabricated using a two‐electrode cell, which displayed a low cell voltage and high stability. In summary, the first iron selenide material is reported that can be used as a bifunctional electrocatalyst for the OER and HER, as well as overall water splitting.