The developed Ni-La/Al2O3-CeO2-Bamboo charcoal (ACB) catalyst was applied to the co-pyrolysis of straw and plastic to produce hydrogen in a horizontal quartz tube pyrolysis furnace. In this study, the effects of the mixing ratio of straw and plastic, the presence and stability of the catalyst on the co-pyrolysis hydrogen production were investigated. Experiment showed that the addition of PE can increase the yield of H2 within a certain range, and the best mass ratio of 5:5 was found. In the co-pyrolysis process with the participation of the catalysts, the macromolecular tar can be cracked into combustible gases such as H2, and the H2 yield could be increased to 332.2ml/g (Ni-La/ACB) is much higher than 68.87ml/g without catalyst. Compared with Ni/ACB, Ni-La/ACB had been increased the alkalinity by adding La element and enhanced the carbon deposition resistance of the catalyst, which makes the catalyst maintain higher stability. This was also confirmed in stability test experiments.