It is a great challenge to fabricate electrode with simultaneous high activity for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Herein, a high‐performance bifunctional electrode formed by vertically depositing a porous nanoplate array on the surface of nickel foam is provided, where the nanoplate is made up by the interconnection of trinary Ni–Fe–Mo suboxides and Ni nanoparticles. The amorphous Ni–Fe–Mo suboxide and its in situ transformed amorphous Ni–Fe–Mo (oxy)hydroxide acts as the main active species for HER and OER, respectively. The conductive network built by Ni nanoparticles provides rapid electron transfer to active sites. Moreover, the hydrophilic and aerophobic electrode surface together with the hierarchical pore structure facilitate mass transfer. The corresponding water electrolyzer demonstrates low cell voltage (1.50 V @ 10 mA cm−2 and 1.63 V @ 100 mA cm−2) with high durability at 500 mA cm−2 for at least 100 h in 1 m KOH. A high‐performance bifunctional electrode in the form of a porous nanoplate array vertically aligned on nickel foam for overall water splitting is provided. The porous nanoplate is built by the interconnection of trinary Ni–Fe–Mo suboxides and Ni nanoparticles, which is featured with amorphous active material and rapid electron/mass transfer.