The development of non-noble metal-based electrocatalysts with high performance for hydrogen evolution reaction and oxygen evolution reaction is highly desirable in advancing electrocatalytic water-splitting technology but proves to be challenging. One promising way to improve the catalytic activity is to tailor the d-band center. This approach can facilitate the adsorption of intermediates and promote the formation of active species on surfaces. This review summarizes the role and development of the d-band center of materials based on iron-series metals used in electrocatalytic water splitting. It mainly focuses on the influence of the change in the d-band centers of different composites of iron-based materials on the performance of electrocatalysis. First, the iron-series compounds that are commonly used in electrocatalytic water splitting are summarized. Then, the main factors affecting the electrocatalytic performances of these materials are described. Furthermore, the relationships among the above factors and the d-band centers of materials based on iron-series metals and the d-band center theory are introduced. Finally, conclusions and perspectives on remaining challenges and future directions are given. Such information can be helpful for adjusting the active centers of catalysts and improving electrochemical efficiencies in future works.