The thermodynamics on the direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH was calculated and analyzed. Using Y(NO3)(3)center dot 6H(2)O 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)center dot 6H(2)O was measured by thermogravimetric analysis, and Y2O3 was obtained after the precursor calcination at desired temperatures, denoted as Y2O3-T (degrees 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 degrees C, 8 MPa, and 6 h, which also exhibited reliable recycle ability.