<p>The Three-Way Catalytic performances of Pd supported on dual-substituted LaFeO₃ catalysts have been studied from temperature-programmed experiments in typical TWC operating conditions. La has been partly substituted by Ca and Fe by Cu. Pd was introduced simply by wet impregnation. Particular attention was paid to the structure and composition of La-substituted by calcium and A-deficient perovskites to stabilize palladium dispersion and oxidation state. Weak interactions between oxidic Pd species and LaFeO₃ lead the prevalence of metallic Pd species which are responsible of the highest metallic Pd dispersion. In contrast, much less reducible oxidic Pd species can be stabilized in defective sites characteristic of La-deficient et Ca-substituted perovskite structures then improving oxygen mobility. The changes in reaction rates, activation energies, and selectivities for oxidation and reduction reactions would solely reflect the participation of Pd as active sites on Pd/LaFeO₃, while the cooperative effect between palladium and surface oxygen species belonging to the perovskite lattice would be responsible for the superior performance of Pd/La_{1− <i>x</i>}Ca_<i>x</i>Fe_0.8Cu_0.2O₃. The practical interest of this composition is emphasized through the comparison with a benchmark Pd/Ce_<i>x</i>Zr_1−<i>x</i>O₂ catalyst.</p>