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.Graphical　AbstractThe　2Pd-4Cu@MIL-101　catalyst　delivers　superior　CO　esterification　activity.　Cu　incorporation　reduces　Pd　size,　confines　Pd　within　MIL-101　pores,　and　enables　electron　transfer　with　Cu　and　Cr-oxo　sites,　thereby　promoting　CO　activation　and　enhancing　catalytic　performance