Nickel catalyst supported on honeycomb cinder (Ni/HC) was prepared by a homogeneous precipitation method. The catalyst was applied to produce hydrogen-rich combustible gas by catalytic pyrolysis of soybean straw and plastic (PE) mixture. The straw and plastic materials were analyzed by elemental analysis and industrial analysis. The support and catalyst were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), and N2 adsorption-desorption isotherm (BET). The analysis showed that NiO was well loaded on the surface of honeycomb coal slag carrier. The effects of Ni loading, pyrolysis temperature, holding time, and calcination temperature on the experimental results were studied. The results showed that the preparation of the catalyst was feasible and that it had a good catalytic effect. When Ni loading was 15 wt.%, catalytic pyrolysis temperature was 700 °C, holding time was 20 min, and calcination temperature of catalyst was 400 °C, H2 concentration increased from 20.6 to 52.8 vol.%, and while H2 yield was 302 mL/g, CH4 concentration decreased from 51.1 to 22.6 vol.% and CO concentration increased from 10.8 to 17.8 vol.%. After the catalyst was regenerated 6 times, the H2 concentration still reached 40 vol.% and the combustible gas concentration was still above 80 vol.%. The catalyst still had good catalytic activity.