CO　esterification　to　dimethyl　carbonate　(DMC)　offers　a　promising　alternative　synthesis　route.　Contrary　to　the　conventional　view　that　Pd(II)　species　serve　as　the　active　centers,　Pd(0)　confined　in　metal–organic　frameworks　(MOFs)　catalyst　was　developed,　which　reversed　product　selectivity　and　enabled　highly　selective　DMC　formation.　Extending　beyond　monometallic　systems,　we　further　investigated　Pd–Cu@MOFs　bimetallic　catalysts,　revealing　that　the　Cu　fraction　plays　a　key　role　in　modulating　catalytic　activity.　A　series　of　2Pd-xCu@MIL-101　(x　=　2,　4,　6)　bimetallic　catalysts　by　loading　Pd-Cu　nanoparticles　(NPs)　into　MIL-101　were　synthesized.　Under　identical　reaction　conditions,　all　2Pd-xCu@MIL-101　catalysts　outperformed　the　2Pd@MIL-101　catalyst.　The　2Pd–4Cu@MIL-101　catalyst　exhibited　the　highest　CO　conversion　activity　(60%),　markedly　surpassing　that　of　the　monometallic　2Pd@MIL-101　catalyst　(38%).　The　experimental　results　demonstrate　that　the　introduction　of　Cu　NPs　decreases　the　particle　size　of　Pd　NPs　and　facilitates　their　incorporation　into　the　mesopores　of　MIL-101.　According　to　the　characterization　results　of　X-ray　photoelectron　spectra　(XPS)　and　in　situ　diffuse　reflectance　infrared　Fourier-transform　spectroscopy　(DRIFTS),　partial　electron　transfer　may　occur　between　Pd　NPs　and　the　Cr-oxo　sites　of　MIL-101　as　well　as　the　incorporated　Cu　species,　thereby　facilitating　CO　activation　and　enhancing　catalytic　activity.　This　work　provides　valuable　insights　for　the　development　of　high-performance　catalysts　for　CO　esterification　to　DMC.　©　The　Author(s),　under　exclusive　licence　to　Springer　Science+Business　Media,　LLC,　part　of　Springer　Nature　2025.