The reaction mechanism of dimethyl carbonate (DMC) production over ZrO₂ from CO₂ and CH₃OH is well-known, but the level of understanding has not improved in the last decade. Most commonly, the reaction mechanism has been explored in the gas phase, whilst DMC production occurs in the liquid phase. To overcome this contradiction, we exploited in situ ATR-IR spectroscopy to study DMC formation over ZrO₂ in the liquid phase. A multiple curve resolution-alternate least square (MCR-ALS) approach was applied to spectra collected during the CO₂/CH₃OH interaction with the catalyst surface, leading to the identification of five pure components with their respective concentration profiles. CO₂ and CH₃OH activation to carbonates and methoxide species was found to strongly depend on the reaction temperature. Low temperature prevents methanol dissociation leaving a catalyst covered with stable carbonates, whilst higher temperature decreases the stability of the carbonates and enhances the formation of methoxides. A reaction path involving the methoxide/carbonate interaction at the surface was observed at low temperature (≤50 °C). We propose that a different reaction path, independent of carbonate formation and involving the direct CO₂/methoxide interplay, occurs at 70 °C.