A series of Pd/gamma-Al2O3 catalysts modified by CeO2 and La2O3 were prepared by impregnation method with different La2O3, CeO2 dope manners. Methanol decomposition was used as a probe reaction. The structure of the catalysts was characterized by means of BET, XRD, XPS and FTIR. The results showed that a La2O3-CeO2 solid solution was facile to form by La3+ dissolution into CeO2 lattice. The dimension of CeO2 particles decreased, while the dispersion and crystal plane of Pd and the Pd-CeO2 interaction varied with La2O3, CeO2 dope manners. High dispersion of Pd and a strong interaction between Pd and CeO2 were observed on a La2O3 and CeO2 modified Pd/Al2O3 catalyst with La2O3-CeO2 successive dope manner, which resulted in high activity for methanol decomposition.