The use of carbon dioxide in the synthesis of chemicals, such as dimethyl carbonate (DMC), constitutes an environmentally attractive alternative to hazardous and toxic reagents. However, the direct synthesis of DMC from methanol and CO2 is characterized by low yields due to the reaction equilibrium and the thermodynamic limitations (ΔG298K 0 = +26.3 kj/mol). Alkoxide ionic liquids possessing alkylimidazolium and benzalkonium cations were prepared, characterised and tested together with ZrO2-MgO catalyst for the synthesis of DMC from methanol and CO 2. By using the novel ionic liquid as additives, ca. 12% conversion of methanol, and 90% selectivity to DMC was obtained at 120 °C and 7.5 MPa. The water abstracting potential of the ionic liquids influenced the conversion of methanol and the selectivity to DMC. The alkoxide ionic liquids were recovered and reused in DMC synthesis without loss in activity and selectivity.