Due to enhanced high-temperature stability, zirconia-stabilized alumina is widely used as a support of three-way catalysts. The addition of barium oxide is known to improve the catalytic performance of the composition. In order to go in-depth about the effects of BaO addition, a series of samples was prepared using nitrates and complex salts as a precursor. The interaction of BaO with alumina was found to change dramatically the metal-support interaction of the latter with metals. Thus, the presence of BaO resulted in the sintering of Pd with the formation of agglomerated Pd0 species, which explains a lower activity in CO oxidation of the BaO-doped samples after thermal treatment. Contrarily, the addition of barium nitrate showed a positive effect, inhibiting the collapse of the porous structure of the support, which was the most crucial and accompanied by the formation of the α-Al2O3 phase when no barium nitrate was added.