Pore-structure stability of pure and Ce-doped alumina in air and argon atmospheres was studied using DTA, TGA, N2 ads./des. and XRD with a view to understand the importance of the ionic size of the dopant cation on the pore-structure stability of alumina. The ionic size effect was studied by heat treating the Ce-alumina system in both oxidizing and reducing atmospheres to have Ce4+ (87 pm) and Ce3+ (106 pm) respectively. No compound formation between Ce and alumina was observed. In the case of pure alumina there is a drastic reduction in porosity during the transformation to α-alumina. Ce-doped alumina has a higher DSC transformation temperature corresponding to the α-alumina transformation compared to pure alumina. Ce-doped alumina showed higher pore-structure stability compared with pure alumina and the stability was relatively higher in reducing atmosphere (higher Ce3+/Ce4+ ratio, higher effective ionic size) compared with oxidizing conditions (lower Ce3+/Ce4+ ratio, lower effective ionic size).