As a clean and renewable energy carrier, hydrogen (H2) has become an attractive alternative to dwindling fossil fuels. The key to realizing hydrogen-based energy systems is to develop efficient and economical hydrogen production methods. The water electrolysis technique has the advantages of cleanliness, sustainability, and high efficiency, which can be applied to large-scale hydrogen production. However, the electrocatalytic oxygen evolution reaction (OER) at the anode plays a decisive role in the efficiency of hydrogen evolution during water splitting. Generally, noble metal catalysts (such as ruthenium and iridium) are considered to exhibit the best OER performance; however, they exhibit disadvantages such as high costs, limited reserves, and poor stability. Therefore, the research on highly efficient non-noble metal catalysts that can replace their noble metal counterparts has always been important. This review presents the recent advances in the preparation of high-performance OER electrocatalysts by regulating the electronic structure of 3d transition metals. First, we introduce the reaction mechanism of water splitting and the OER, which reveals the high requirement of the complex four-electron process of the OER. Second, the electron transfer mode and development progress of highly active transition metal electrocatalysts are used to summarize the research situation of transition metal OER catalysts in water splitting. Finally, the future development direction and challenges of transition metal catalysts are prospected based on the current research progress.