Designing controlled hybrid nanoarchitectures between plasmonicand catalytic materials is of paramount importance to fully exploit each function of constituent materials. This study reports a new synthetic strategy for the realization of colloidal clusters of core-shell nanoparticles with plasmonic cores and catalytically active shells. The Au@M (M = Pd or Pt) nanoparticle clusters (NPCs) with a high density of sub-1 nm interparticle gaps are successfully prepared by the deposition of M shells onto thermally activated Au NPCs. NPCs with other metal, metal sulfide, and metal oxide shells can also be synthesized by using the present approach. The prepared Au@M NPCs show remarkably enhanced plasmonic performance compared to their Au@M nanoparticle counterparts due to the localization of a strong electromagnetic field at the interparticle gaps, while the inherent catalytic function of shells is intact. In situ real-time Raman spectroscopy and plasmon-enhanced electro-catalysis experiments demonstrate that the controlled assembly of core-shell nanoparticles is a very effective route for the synergistic integration of plasmonic and catalytic functions in a single platform.