The catalytic combustion of methane is a key reaction taking place on Natural Gas Vehicle three-way catalysts in unfavorable stoichiometric and rich operating conditions. Pd-doped LaxMnO3 based materials have been developed. Their efficacy has been studied on the basis of the following parameters: La-composition (x = 0.7 or 1), homogeneity of perovskite composition according to the protocol synthesis (sol–gel vs. combustion method), strategy for Pd incorporation. The control of Pd dispersion is closely related to the method used for Pd addition. Stabilization of Pd inside the perovskite lattice through a sol–gel route outperforms classical wet impregnated samples in terms of catalytic activity. This trend is accentuated on La-deficient composition as the creation of defective sites can strengthen the Pd–LaxMnO3 interaction. The best compromise was found on La0.7Mn0.98Pd0.02O3.