This study investigated catalytic reforming, which is a thermochemical process, as a pioneering method to treat biogas slurry (wastewater from biogas plants) and generate hydrogen. Experimental validation for treating biogas slurries from digested cattle manure, fish intestine, and wheat straw was performed on Ni/α-Al2O3 catalyst. The results showed that the total organic carbon, total nitrogen, and PO43- ion contents in biogas slurry could be reduced by 98.69, 98.01, and 99.32%, respectively. The highest hydrogen yield was obtained in the treatment of biogas slurry from digested cattle manure at 750 °C, in which the hydrogen yield and hydrogen concentration were 13.85 Lhydrogen/LBS and 79.77 vol %, respectively. Changes in the crystalline phase and structure of the catalyst were observed during catalytic reforming of biogas slurry. Active metal oxidization and carbon deposition were likely to be important factors affecting catalytic stability. The mass flow evaluation verified the hydrogen generation potential by the catalytic reforming of biogas slurry, which was close to the methane generation capability of the upstream biogas plant. However, additional effort is required to address the high energy consumption of this method. These findings provide fundamental knowledge about the potential of applying thermochemical techniques to treat and utilize high total organic carbon-containing wastewaters.