The catalytic yields of POM to hydrogen over M(1)-Ni(5)/AlCeO3 (M = La, Ce, Y) were investigated using a fixed bed flow reactor under atmosphere. The crystal phase behavior of reduced La(1)-Ni(5)/AlCeO3 catalysts before and after the reaction were studied via XRD analysis. FESEM and EDS analyses were further performed to show the uniformed distribution of La, Ni, and Ce metal particles on the catalyst surface. XPS results showed O2-, O2 2- species and metal ions such as Ce3+, Ce4+, La3+ and Ni2+ etc. were on the catalyst surface. When 1 wt% of La was added to Ni(5)/AlCeO3 catalyst, Ni2p3/2 and Ce3d5/2 increased 52.7 and 6.3%, respectively. The yield of hydrogen on the La(1)-Ni(5)/AlCeO3 catalyst was 89.1%, which was much better than that of M(1)-Ni(5)/AlCeO3 (M = Ce, Y). As Ce4+ ions of CeO2 produced by the reaction of AlCeO3 with oxygen were substitute to La3+, it made oxygen vacancies in the lattice and further improved the hydrogen yield by increasing the dispersion of Ni atoms with strong metal-support interaction (SMSI) effect.