Orbital hybridization to regulate the electronic structures and surface chemisorption properties of transition metals has been extensively investigated for searching high-performance catalysts toward various reactions. Unlike conventional d-d hybridization, the d-sp hybridization interaction between transition metals and p-block elements could result in surprising electronic properties and catalytic activities. This feature article highlights the recent progress in the development of high-performance transition metal-based catalysts through the extraordinary d-sp hybridization strategy, particularly for energy-related electrocatalytic applications. We start by giving an introduction of fundamental concepts associated with electronic structures of transition metal catalysts, including the Sabatier principle, d-band theory, electronic descriptor, as well as the comparison of d-d hybridization and d-sp hybridization strategies. Then, we summarize the theoretical and experimental advances in d-sp hybridization catalysts, including p-block element-doped metal catalysts, intermetallic catalysts and supported metal catalysts, with emphasis on the important roles of d-sp hybridization in tuning catalytic performances. Finally, we present existing challenges and future development prospects for the rational design of advanced d-sp hybridization catalysts.