Recyclable nanocatalysts of core-shell bimetallic nanocrystals are developed through polydopamine coating-directed one-step seeded growth, interfacial assembly, and substrate-immobilization of Au@Ag core-shell nanocrystals. This strategy provides new opportunities to design and optimize heterogeneous nanocatalysts with tailored size, morphology, chemical configuration, and supporting substrates for metal-catalyzed reactions.