Structurally ordered intermetallic borides are a large family of inorganic solids with rich bonding schemes, and huge compositional and structural diversity. The family members possess high flexibility to modulate the local electronic structures and surface adsorption properties, providing great opportunities for the development of advanced catalysts with superior activity and stability. In this review, we summarize the structural features of intermetallic borides, with emphasis on the covalent linkage patterns of boron atoms in them, and the research methods for understanding their electronic structures. We also present the recent developments in the synthesis of phase-pure, well-defined intermetallic borides, most of which are suitable for catalytic studies. We further highlight the theoretical and experimental advances in the emerging boride-catalyzed reactions and the important roles of boron in tuning electrocatalytic performances. Finally, we propose the remaining challenges and future developments of boride synthesis and catalytic applications.