Burning fossil fuels account for over 75% of global greenhouse gas emissions and over 90% of carbon dioxide emissions, calling for alternative fuels such as hydrogen. Since the hydrogen demand could reach 120 million tons in 2024, efficient and large-scale production methods are required. Here we review electrocatalytic water splitting with a focus on reaction mechanisms, transition metal catalysts, and optimization strategies. We discuss mechanisms of water decomposition and hydrogen evolution. Transition metal catalysts include alloys, sulfides, carbides, nitrides, phosphides, selenides, oxides, hydroxides, and metal-organic frameworks. The reaction can be optimized by modifying the nanostructure or the electronic structure. We observe that transition metal-based electrocatalysts are excellent catalysts due to their abundant sources, low cost, and controllable electronic structures. Concerning optimization, fluorine anion doping at 1 mol/L potassium hydroxide yields an overpotential of 38 mV at a current density of 10 mA/cm². The electrocatalytic efficiency can also be enhanced by adding metal atoms to the nickel sulfide framework.