Molybdenum phosphide (MoP) has received increasing attention for the hydrogen evolution reaction (HER) due to its Pt-like electronic structure and high electrical conductivity. In this work, a flake-like Ru-doped MoP with phosphorus vacancy (Ru-MoP-P V ) electrocatalyst is synthesized for the first time by a simple and rapid room-temperature microwave approach within 30 s. The created abundant phosphorus vacancies provide rich active sites and favor rapid electron transfer. The introduced Ru also enhances the catalytic activity of the synthesized electrocatalyst efficiently. Then, the designed Ru-MoP-P V possesses low overpotentials for HER with 79, 100, and 161 mV in 1.0 M KOH, 0.5 M H 2 SO 4 , and 1.0 M phosphatebuffered saline to obtain 10 mA cm −2 . The Ru-MoP-P V and NiFelayered double hydroxide are used as the cathode and the anode, respectively, to drive water splitting and just need a low cell voltage of 1.6 V to achieve 10 mA cm −2 . This work provides a feasible way for the rapid production of metal phosphides for energy conversion and storage applications.