In the field of renewable energy, the splitting of water into hydrogen and oxygen fuel gases using water electrolysis is a prominent topic. Traditionally, these catalytic processes have been performed by platinum‐group metal catalysts, which are effective at promoting water electrolysis but expensive and rare. The search for an inexpensive and Earth‐abundant catalyst has led to the development of 3d‐transition‐metal phosphides for the hydrogen evolution reaction. These catalysts have shown excellent activity and stability. In this review, we discuss the electronic and crystal structures of bulk and surface of selected Fe, Co, and Ni phosphides, and their relationships to the experimental catalytic activity. The various synthetic protocols towards the state‐of‐the‐art transition metal phosphide electrocatalysts are also discussed.