Atomically　precise　metal　nanoclusters　(NCs)　have　garnered　significant　interest　due　to　their　unique　atomic　stacking　structures,　the　effect　of　quantum　confinement,　and　enriched　active　sites　but　suffer　from　thermal-　or　light-induced　poor　instability　and　self-aggregation,　together　with　in　situ　self-conversion　to　conventional　metal　nanoparticles　(NPs).　How　to　effectively　harness　the　generic　detrimental　self-transformation　property　of　metal　NCs　has　so　far　not　garnered　immense　attention　within　the　realm　of　catalysis.　In　this　work,　we　develop　a　layer-by-layer　assembly　technology　to　accurately　anchor　metal　NCs　to　the　metal　oxide　matrix.　Then,　the　anchoring　of　metal　NCs　to　metal　NPs　is　triggered　by　a　simple　thermal　treatment　that　enables　precise　control　over　the　interface　structure,　resulting　in　a　hollow　core-shell　heterostructure　with　a　metal　core　(Au,　Ag)　encapsulated　by　a　metal　oxide　(CeO2,　Fe2O3,　SnO2)　shell.　Benefiting　from　the　synergistic　interplay　between　metal　NPs　and　the　metal　oxide　substrate,　such　self-assembled　metal　NPs@metal　oxide　heterostructures　display　excellent　catalytic　activities　and　stability　in　the　reduction　of　aromatic　nitro　compounds.　The　detailed　catalytic　mechanism　is　elucidated.　Our　work　offers　fresh　impetus　for　the　judicious　utilization　of　the　inherent　instability　of　metal　NCs　for　catalytic　selective　organic　transformation.　©　2024　American　Chemical　Society.