Herein, we develop a series etching and atom codeposition process to fabricate concave double-shell AgAu (CD-AgAu) and CD-AgAu:Pd nanocubes. High surface area and edge activity from the CD nanostructure consisting of a single hole appear in the central area, and 12 concave structures exhibit superior surface-enhanced Raman scattering (SERS). As investigating the Pd dopants at the CD surface with SERS and electrochemistry, we demonstrate that the 2.8% Pd-doped CD-AgAu nanocubes perform impressive catalysis at ≤30 s of the hydrogenation reaction by lowering the activation energy. Furthermore, the CD-AgAu:4.6%Pd nanocubes act as a superior catalyst for glycerol electrooxidation and could retain their highindex facets after a long-term durability test. Our work will help to motivate future efforts for the deliberate incorporation of a low content of noble metals into CD nanostructures to develop chemical sensing devices in interfacial reactions and clean energy conversion technology.