Abstract Designing palladium‐based formic acid oxidation reaction (FAOR) catalysts to achieve significant breakthroughs in catalytic activity, pathway selectivity, and toxicity resistance is both urgent and challenging. Here, these challenges are addressed by pioneering a novel catalyst design that incorporates both topological and chemical disorder, developing a new class of PdCuLaYMnW high‐entropy amorphous alloys with a porous network (Net‐Pd‐HEAA) as a highly active, selective, and stable FAOR electrocatalyst. This novel Net‐Pd‐HEAA demonstrates record‐breaking FAOR performance, achieving the mass and specific activities of 5.94 A mg Pd −1 and 8.94 mA cm −2 , respectively, surpassing all previously reported Pd‐based catalysts and showing strong competitiveness against advanced Pt‐based catalysts. Simulataneously, Net‐Pd‐HEAA exhibits extraordinary stability in accelerated durability tests (ADT) and chronoamperometry (CA) tests. Advanced characterization and in situ, spectral analysis reveal that the extremely disordered atomic structure effectively regulates the geometric and electronic structure of the Pd sites, enhancing active intermediate coverage, facilitating dehydrogenation pathway, and inhibiting the production/adsorption of CO. Furthermore, when employed as the anode catalyst in proton exchange membrane water electrolysis (PEMWE), Net‐Pd‐HEAA only requires a potential of 1.28 V to obtain a current density of 1 A cm −2 , and operates stably in a highly corrosive electrolyte for over 100 h.

Engineering Topological and Chemical Disorder in Pd Sites for Record‐Breaking Formic Acid Electrocatalytic Oxidation