AbstractIntermetallic nanomaterials have shown promising potential as high‐performance catalysts in various catalytic reactions due to their unconventional crystal phases with ordered atomic arrangements. However, controlled synthesis of intermetallic nanomaterials with tunable crystal phases and unique hollow morphologies remains a challenge. Here, a seeded method is developed to synthesize hollow PdSn intermetallic nanoparticles (NPs) with two different intermetallic phases, that is, orthorhombic Pd₂Sn and monoclinic Pd₃Sn₂. Benefiting from the rational regulation of the crystal phase and morphology, the obtained hollow orthorhombic Pd₂Sn NPs deliver excellent electrocatalytic performance toward glycerol oxidation reaction (GOR), outperforming solid orthorhombic Pd₂Sn NPs, hollow monoclinic Pd₃Sn₂ NPs, and commercial Pd/C, which places it among the best reported Pd‐based GOR electrocatalysts. The reaction mechanism of GOR using the hollow orthorhombic Pd₂Sn as the catalyst is investigated by operando infrared reflection absorption spectroscopy, which reveals that the hollow orthorhombic Pd₂Sn catalyst cleaves the CC bond more easily compared to the commercial Pd/C. This work can pave an appealing route to the controlled synthesis of diverse novel intermetallic nanomaterials with hollow morphology for various promising applications.