The methoxycarbonylation of anilines stands as an attractive method for the phosgene‐free production of carbamates. Despite the high yields reported for ceria as catalyst, the reduction of the amount of side products and the prevention of catalyst deactivation still represent major hurdles in this chemistry. One advantage of ceria is the possibility of tuning its reactivity by doping its lattice with other metals. A series of doped ceria‐based materials, prepared by substitution with metals, are evaluated in the methoxycarbonylation of 2,4‐diaminotoluene with dimethylcarbonate. Among all catalysts, containing Eu, Hf, La, Pr, Sm, Tb, Y or Zr oxides, ceria with 2 mol% ZrO2 exhibited 96% selectivity towards the desired carbamates, improving the CeO2 catalyst. Density functional theory demonstrates that two descriptors are needed: (i) a geometric factor that governs the reduction of energy barriers for carbamate formation through ureas; (ii) catalyst basicity as N‐H bonds need to be activated. Assessment in subsequent reaction cycles revealed that the CeO2/ZrO2 catalyst is more stable than bulk CeO2, along with the reduction of fouling processes.