A computer simulation study of the Ce4+/Ce3+ reduction process in CeO2-MO (M = Ca, Mn, Ni, Zn) and CeO2-M2O3 (M = Sc, Mn, Y, Gd, La) mixed oxides is presented. Calculations satisfactorily reproduce the observed structural parameters of the solid solutions over a wide range of compositions. On energetic grounds, the Ce4+/Ce3+ reduction process is enhanced with increasing dopant content, with the enhancement being more pronounced for divalent dopants. For a fixed dopant level, the reduction of cerium is more favorable for larger dopant ions. The results are explained in terms of the higher oxygen vacancy concentration and the larger dopant size being effective in accommodating the greater relaxation or elastic strain associated with forming the larger Ce3+ species upon reduction.