Ni-Co/-Al2O3, Ni/-Al2O3, Co/-Al2O3, mechanical mixed Ni/-Al2O3, and Co/-Al2O3 catalyst (another name is Ni/-Al2O3|Co/-Al2O3) were prepared by the wet impregnation method, and the catalytic performance for hydrogen production by catalytic reforming of volatile from biomass pyrolysis over the four catalysts was compared under the condition of different temperatures and weight hourly space velocity. The experimental results show that the catalytic performance of the four catalysts from high to low is Ni-Co/-Al2O3 > Co/-Al2O3 > Ni/-Al2O3|Co/-Al2O3 > Ni/-Al2O3 within the studied temperature and weight hourly space velocity scope. Hydrogen selectivity of 94.83% and hydrogen yield of 120.81 g/kg biomass (dry basis) were obtained over Ni-Co/-Al2O3 under the condition of catalytic reforming temperature of 825 degrees C and weight hourly space velocity of 0.71 h(-1).