The　thermodynamics　on　the　direct　synthesis　of　dimethyl　carbonate　(DMC)　from　CO2　and　CH3OH　was　calculated　and　analyzed.　Using　Y(NO3)3·6H2O　as　the　precursor,　a　series　of　Y2O3　were　prepared　through　the　one-pot　calcination　method,　which　were　employed　to　catalyze　DMC　synthesis.　The　decomposition　temperature　of　Y(NO3)3·6H2O　was　measured　by　thermogravimetric　analysis,　and　Y2O3　was　obtained　after　the　precursor　calcination　at　desired　temperatures,　denoted　as　Y2O3-T　(°C).　The　catalysts　were　characterized　by　X-ray　diffraction,　Brunauer-Emmett-Teller　method,　transmission　electron　microscopy,　NH3/CO2　temperature-programmed　desorption,　and　X-ray　photoelectron　spectroscopy　to　detect　the　crystal　phase,　surface　property,　particle　size,　acidity-basicity　amounts,　and　oxidation　state,　respectively.　The　characterization　results　indicated　that　Y2O3-750　can　favor　the　formation　of　moderate　acidic　and　basic　sites　and　facilitate　the　activation　of　CO2　and　CH3OH.　The　catalytic　performance　evaluation　was　experimentally　investigated,　and　Y2O3-750　owned　the　highest　DMC　yield　of　1.02　mmol/g·cat　under　90　°C,　8　MPa,　and　6　h,　which　also　exhibited　reliable　recycle　ability.　Copyright　©　2020　American　Chemical　Society.