That dimethyl carbonate is directly synthesized from methanol and carbon dioxide is an effective and environmental approach to solve the greenhouse effect. For the sake of solving the problems of low DMC productivity and poor catalysts stability in presence of the formed water. Here we design and prepare a serial of spherical La-doped ceria nanoparticles (Ce1-xLaxOδ nanocomposites, x=0.00, 0.05, 0.10, 0.15, and 0.20) via a co-precipitation method. These Ce1-xLaxOδ composites are ground into slurry by ball milled and then coated on cordierite honeycomb ceramics to obtain Ce1-xLaxOδ monolithic catalysts. These Ce1-xLaxOδ composites are characterized extensively by TEM, XRD, Raman spectroscopy, N2 adsorption-desorption isotherms, H2-TPR and XPS. The characterization results show that the Ce1-xLaxOδ composites nanoparticles possesses richer surface oxygen vacancies, higher BET surface area and smaller particle size than that of pure CeO2 nanoparticle. Besides, catalytic activity test shows these Ce1-xLaxOδ monolithic catalysts exhibit better catalytic performance than that of pure CeO2 nanoparticles. Among them, Ce0.95La0.05Oδ monolithic catalyst exhibits the highest CH3OH conversion and DMC yield, which is in good line with the oxygen vacancy content measured by XPS. Finally, the Ce0.95La0.05Oδ monolithic catalyst also shows an excellent durability of more than 100 hours, which is mainly due to the doping effect of lanthanum into the ceria oxides tailoring the structure and surface properties of the catalyst.